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US7943517B2 - Semiconductor device with a barrier film - Google Patents

Semiconductor device with a barrier film Download PDF

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Publication number
US7943517B2
US7943517B2 US11/877,243 US87724307A US7943517B2 US 7943517 B2 US7943517 B2 US 7943517B2 US 87724307 A US87724307 A US 87724307A US 7943517 B2 US7943517 B2 US 7943517B2
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film
interconnection
main
insulating film
layer
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US20080057704A1 (en
Inventor
Junichi Koike
Makoto Wada
Shingo Takahashi
Noriyoshi Shimizu
Hideki Shibata
Satoshi Nishikawa
Takamasa Usui
Hayato Nasu
Masaki Yoshimaru
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Renesas Electronics Corp
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Semiconductor Technology Academic Research Center
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Priority to US13/087,026 priority patent/US8133813B2/en
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
    • C02F11/126—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using drum filters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
    • H01L21/76844—Bottomless liners
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • H01L21/76829—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
    • H01L21/76831—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers in via holes or trenches, e.g. non-conductive sidewall liners
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
    • H01L21/76849—Barrier, adhesion or liner layers formed in openings in a dielectric the layer being positioned on top of the main fill metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
    • H01L21/76855—After-treatment introducing at least one additional element into the layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
    • H01L21/76855—After-treatment introducing at least one additional element into the layer
    • H01L21/76856—After-treatment introducing at least one additional element into the layer by treatment in plasmas or gaseous environments, e.g. nitriding a refractory metal liner
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76867—Barrier, adhesion or liner layers characterized by methods of formation other than PVD, CVD or deposition from a liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
    • H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
    • H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
    • H01L23/53204—Conductive materials
    • H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
    • H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
    • H01L23/53238—Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a semiconductor device including an interconnection, which has an interconnection main layer containing Cu (copper) as the main component (i.e., by 50% or more), wherein such an interconnection will be also referred to as a Cu interconnection, for the sake of convenience.
  • the present invention also relates to a semiconductor device manufacturing method for forming such an interconnection by a barrier self-formation process.
  • the present invention relates to a semiconductor device and manufacturing method thereof, utilizing a damascene interconnection structure.
  • interconnection structures employing Cu and an insulating film with a low dielectric constant have been developed to increase the speed and integration degree of silicon (Si) semiconductor integrated circuits.
  • the Cu interconnection easily causes counter diffusion relative to an insulating layer around it, or easily causes a reaction in an oxygen atmosphere and produces a Cu oxide film, during various heat treatments used for manufacturing the integrated circuit.
  • a diffusion barrier film such as a tantalum (Ta) or tantalum nitride (TaN) film, before the Cu layer (interconnection main layer) is formed.
  • a diffusion barrier film such as a tantalum (Ta) or tantalum nitride (TaN) film
  • barrier films are required to be thinner with generation changes to reduce the interconnection resistance, because the interconnection width will decrease, thereby increasing the resistance.
  • conventional barrier film formation methods entail some difficulties in depositing a barrier film on the side surface of an interconnection groove or via hole (interconnection hole) with uniform thickness and quality. As a consequence, it is difficult to ensure a required barrier property level of the barrier film, the adhesiveness at the interface between the barrier film and Cu layer, and the resistance against electromigration due to interface diffusion, thereby causing problems in reliability.
  • a barrier less structure which does not include any conventional barrier film formation process, is conceivable. It has been proposed, as a method of forming a barrier less structure, to add an alloy element in a Cu layer and perform a heat treatment on the Cu layer, so as to diffuse the alloy element to the interface between the Cu layer and an insulating layer, at which the alloy element reacts with the insulating layer and thereby forms a stable compound.
  • a barrier film is required to ensure the reliability of the structure.
  • the presence of the barrier film brings about problems, such as an increase in interconnection resistance, and a decrease in interconnection reliability.
  • a barrier less structure is expected as an ultimate interconnection structure, such a structure is very difficult to achieve. Accordingly, it is desired to provide a semiconductor device and manufacturing method thereof which can improve the reliability of an interconnection structure and decrease the interconnection resistance.
  • a semiconductor device comprising:
  • the barrier film interposed between the interlevel insulating film and the interconnection main layer within the opening, the barrier film containing, as a main component, a compound of a predetermined metal element with a component element of the interlevel insulating film.
  • a method of manufacturing a semiconductor device comprising:
  • the main film containing, as a main component, Cu used as a material of an interconnection main layer;
  • the barrier film containing, as a main component, a compound of the predetermined metal element with a component element of the interlevel insulating film.
  • a method of manufacturing a semiconductor device comprising:
  • the main film containing, as a main component, Cu used as a material of an interconnection main layer;
  • the barrier film containing, as a main component, a compound of the predetermined metal element with a component element of the interlevel insulating film.
  • FIGS. 1A to 1C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a first embodiment of the present invention
  • FIGS. 2A to 2C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a second embodiment of the present invention.
  • FIGS. 3A to 3C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a third embodiment of the present invention.
  • FIGS. 4A to 4C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a fourth embodiment of the present invention.
  • FIGS. 5A to 5C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a fifth embodiment of the present invention.
  • FIGS. 6A to 6C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a sixth embodiment of the present invention.
  • FIGS. 7A to 7C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a seventh embodiment of the present invention.
  • FIGS. 8A to 8C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to an eighth embodiment of the present invention.
  • FIGS. 9A to 9C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a ninth embodiment of the present invention.
  • FIGS. 10A to 10C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a tenth embodiment of the present invention.
  • FIGS. 11A to 11C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to an eleventh embodiment of the present invention.
  • FIGS. 12A to 12C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a twelfth embodiment of the present invention.
  • FIGS. 13A to 13C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a thirteenth embodiment of the present invention.
  • FIG. 14 is a view showing characteristics of various Cu alloys, in terms of change in resistivity relative to heat treatment temperature
  • FIG. 15 is a view showing a TEM micrographic image of a cross section of a semiconductor device manufactured by the first embodiment
  • FIGS. 16A to 16F are sectional views showing sequential steps of a semiconductor device manufacturing method according to a fourteenth embodiment of the present invention.
  • FIG. 17 is a sectional view showing a semiconductor device according to a modification of the fourteenth embodiment.
  • FIG. 18 is a sectional view showing a semiconductor device according to a fifteenth embodiment of the present invention.
  • FIGS. 19A to 19C are sectional views showing sequential steps of a semiconductor device manufacturing method according to a sixteenth embodiment of the present invention.
  • FIGS. 20A to 20E are sectional views showing sequential steps of a semiconductor device manufacturing method according to a seventeenth embodiment of the present invention.
  • FIG. 21 is a graph showing the oxygen concentration distribution in a diffusion prevention film according to a modification of the seventeenth embodiment
  • FIGS. 22A to 22E are sectional views showing sequential steps of a semiconductor device manufacturing method according to an eighteenth embodiment of the present invention.
  • FIG. 23 is a sectional view showing a semiconductor device according to a modification of the eighteenth embodiment.
  • FIGS. 24A to 24F are sectional views showing sequential steps of a semiconductor device manufacturing method according to a nineteenth embodiment of the present invention.
  • FIG. 25 is a sectional view showing a semiconductor device according to a modification of the fourteenth embodiment.
  • a barrier film for preventing Cu diffusion is formed by means of self alignment between an interconnection main layer containing Cu as the main component (i.e., by 50% or more) and an interlevel insulating film.
  • This barrier film contains a compound of a predetermined metal element ⁇ with a component element of the interlevel insulating film.
  • the predetermined metal element ⁇ may comprise at least one element selected from the group consisting of Mn, Nb, Zr, Cr, V, Y, Tc, and Re, and preferably comprise Mn.
  • the metal elements listed above to be usable as the predetermined metal element ⁇ have the following advantages, as compared to Ti and Ta, which are used for conventional barrier films, and Al, Mg, and Sn, which have been proposed by conventional barrier less process techniques. Specifically, the metal elements listed above for the metal element ⁇ can easily form an oxide and the oxide is high in affinity with interlevel insulating films. Accordingly, they can provide a stable oxide layer with uniform quality and very small thickness between an interconnection main layer and an interlevel insulating film. Further, since these elements tend to precipitate or form a compound, rather than staying as solid solution in Cu, they do not increase the interconnection resistance.
  • the interlevel insulating film may comprise O and at least one element selected from the group consisting of Si, C, and F. More specifically, the interlevel insulating film may be made of SiO 2 , SiO x C y , SiO x C y H z , or SiO x F y .
  • the barrier film may contain, as the main component, a material selected from the group consisting of ⁇ x O y , ⁇ x Si y O z , ⁇ x C y O z , and ⁇ x F y O z , where ⁇ denotes the predetermined metal element ⁇ described above.
  • FIGS. 1A to 1C to a set of FIGS. 13A to 11 respectively show semiconductor device manufacturing methods according to different embodiments of the present invention, by sectional views showing the basic arrangement of sequential steps thereof.
  • the material of an interconnection main layer is Cu
  • the metal element ⁇ for a barrier film is Mn
  • the material of the barrier film is MnO.
  • an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO 2 .
  • an alloy film 13 made of Cu and Mn (auxiliary film containing a predetermined metal element ⁇ ) is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12 .
  • the alloy film 13 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm.
  • the Mn content in the alloy film 13 is set to be 0.05 to 20 at % (atomic percentage).
  • the alloy film 13 works as a seed layer for forming a Cu main film by electrolytic plating described later.
  • a heat treatment is performed on the structure shown in FIG. 1A , at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
  • Mn in the alloy film 13 is supplied with a force in directions to remove it from Cu, and thereby diffuses onto the surface of the interlevel insulating film 11 facing the alloy film 13 .
  • Mn thus supplied from the alloy film 13 reacts with O used as a component element of the interlevel insulating film 11 .
  • O used as a component element of the interlevel insulating film 11 As a consequence, as shown in FIG.
  • a barrier film 14 containing, as the main component, a very stable compound or oxide made of MnO is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11 , and have a thickness of 5 nm or less, e.g., 2 nm.
  • the portion of the alloy film 13 on the reverse side to the interlevel insulating film 11 is transformed into a Cu film 15 with a low Mn content.
  • a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a .
  • the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by a planarization process, such as CMP (Chemical Mechanical Polishing), so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12 .
  • CMP Chemical Mechanical Polishing
  • an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO 2 .
  • an alloy film 13 made of Cu and Mn (auxiliary film containing a predetermined metal element ⁇ ) is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12 .
  • the alloy film 13 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm.
  • the Mn content in the alloy film 13 is set to be 0.05 to 20 at % (atomic percentage).
  • a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a .
  • a heat treatment is performed on the structure shown in FIG. 2B , at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
  • a barrier film 14 containing, as the main component, a very stable compound or oxide made of MnO is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11 , and have a thickness of 5 nm or less, e.g., 2 nm.
  • the portion of the alloy film 13 on the reverse side to the interlevel insulating film 11 is essentially integrated with the interconnection main layer formed of the Cu layer 16 a.
  • the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12 .
  • an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO 2 .
  • a Cu film 17 and a Mn film 18 are formed in this order on the interlevel insulating film 11 to cover the inner surface of the groove 12 .
  • the Cu film 17 and Mn film 18 compose an auxiliary film with a multi layered structure containing a predetermined metal element ⁇ .
  • the Cu film 17 and Mn film 18 are formed by, e.g., sputtering to have a thickness of 5 to 100 nm and a thickness of 5 to 100 nm, respectively.
  • a heat treatment is performed on the structure shown in FIG. 3A , at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
  • Mn in the Mn film 18 diffuses onto the surface of the interlevel insulating film 11 facing the Cu film 17 .
  • Mn thus supplied from the Mn film 18 reacts with O used as a component element of the interlevel insulating film 11 .
  • O used as a component element of the interlevel insulating film 11 As a consequence, as shown in FIG.
  • a barrier film 14 containing, as the main component, a very stable compound or oxide made of MnO is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11 , and have a thickness of 5 nm or less, e.g., 2 nm.
  • a Cu film 15 with a low Mn content is formed on the side of the barrier film 14 reverse to the interlevel insulating film 11 .
  • a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a .
  • the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12 .
  • an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO 2 .
  • a Cu film 17 and a Mn film 18 are formed in this order on the interlevel insulating film 11 to cover the inner surface of the groove 12 .
  • the Cu film 17 and Mn film 18 compose an auxiliary film with a multi layered structure containing a predetermined metal element ⁇ .
  • the Cu film 17 and Mn film 18 are formed by, e.g., sputtering to have a thickness of 5 to 100 nm and a thickness of 5 to 100 nm, respectively.
  • a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a .
  • a heat treatment is performed on the structure shown in FIG. 4B , at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
  • a barrier film 14 containing, as the main component, a very stable compound or oxide made of MnO is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11 , and have a thickness of 5 nm or less, e.g., 2 nm.
  • the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12 .
  • an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO 2 .
  • a Mn film 18 and a Cu film 17 are formed in this order on the interlevel insulating film 11 to cover the inner surface of the groove 12 .
  • the Mn film 18 and Cu film 17 compose an auxiliary film with a multi layered structure containing a predetermined metal element ⁇ .
  • the Mn film 18 and Cu film 17 are formed by, e.g., sputtering to have a thickness of 5 to 100 nm and a thickness of 5 to 100 nm, respectively.
  • a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a .
  • a heat treatment is performed on the structure shown in FIG. 5B , at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
  • Mn in the Mn film 18 diffuses onto the surface of the interlevel insulating film 11 facing the Mn film 18 .
  • Mn thus supplied from the Mn film 18 reacts with O used as a component element of the interlevel insulating film 11 .
  • a barrier film 14 containing, as the main component, a very stable compound or oxide made of MnO is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11 , and have a thickness of 5 nm or less, e.g., 2 nm.
  • the Cu film 17 is essentially integrated with the interconnection main layer formed of the Cu layer 16 a.
  • the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12 .
  • a heat treatment for diffusing Mn may be performed before forming the Cu main film 16 , as in the first and third embodiments.
  • an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO 2 .
  • a Mn film (auxiliary film containing a predetermined metal element ⁇ ) 18 is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12 .
  • the Mn film 18 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm.
  • a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a .
  • a heat treatment is performed on the structure shown in FIG. 6B , at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
  • a barrier film 14 containing, as the main component, a very stable compound or oxide made of MnO is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11 , and have a thickness of 5 nm or less, e.g., 2 nm.
  • the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12 .
  • a heat treatment for diffusing Mn may be performed before forming the Cu main film 16 , as in the first and third embodiments.
  • an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO 2 .
  • an alloy film 13 made of Cu and Mn (auxiliary film containing a predetermined metal element ⁇ ) is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12 .
  • the alloy film 13 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm.
  • the Mn content in the alloy film 13 is set to be 0.05 to 20 at % (atomic percentage).
  • a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a .
  • a heat treatment is performed on the structure shown in FIG. 7B , at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
  • the heat treatment is performed within an atmosphere containing oxygen, such as an inactive gas atmosphere of, e.g., Ar, containing O 2 at a volume ratio of 1 ppm to 10%.
  • Mn in the alloy film 13 is supplied with a force in directions to remove it from Cu, and thereby diffuses onto the surface of the interlevel insulating film 11 facing the alloy film 13 , and also diffuses to the upper surface of the Cu main film 16 .
  • Mn thus supplied from the alloy film 13 reacts with O used as a component element of the interlevel insulating film 11 , and with O present within the heat treatment atmosphere.
  • a barrier film 14 containing MnO as the main component is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11 , and have a thickness of 5 nm or less, e.g., 2 nm.
  • an insulating film (reaction product film) 19 containing MnO as the main component is also formed to cover the upper surface of the Cu main film 16 .
  • the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed along with the insulating film 19 by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12 .
  • CMP e.g., CMP
  • Mn since Mn also diffuses to the upper surface of the Cu main film 16 , Mn is scarcely left in the Cu layer 16 a , thereby preventing an increase in interconnection resistance.
  • the auxiliary film containing a predetermined metal element ⁇ may be a multi layered structure formed of a Cu film 17 and a Mn film 18 , as in the fourth embodiment. Also in this modification, a heat treatment for diffusing Mn is performed within an atmosphere containing oxygen, so that the same effects can be obtained.
  • an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO 2 .
  • an alloy film 13 made of Cu and Mn (auxiliary film containing a predetermined metal element ⁇ ) is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12 .
  • the alloy film 13 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm.
  • the Mn content in the alloy film 13 is set to be 0.05 to 20 at % (atomic percentage).
  • a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a .
  • an upper insulating film 20 containing oxygen such as a SiO 2 film, or SiC, SiCN, or SiN film containing oxygen, is formed on the upper surface of the Cu main film 16 .
  • a heat treatment is performed on the structure shown in FIG. 8B , at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
  • Mn in the alloy film 13 is supplied with a force in directions to remove it from Cu, and thereby diffuses onto the surface of the interlevel insulating film 11 facing the alloy film 13 , and also diffuses to the upper surface of the Cu main film 16 .
  • Mn thus supplied from the alloy film 13 reacts with O used as a component element of the interlevel insulating film 11 , and with O used as a component element of the upper insulating film 20 .
  • a barrier film 14 containing MnO as the main component is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11 , and have a thickness of 5 nm or less, e.g., 2 nm.
  • an insulating film (reaction product film) 19 containing MnO as the main component is also formed to cover the upper surface of the Cu main film 16 .
  • the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed along with the insulating film 19 and upper insulating film 20 by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12 .
  • the auxiliary film containing a predetermined metal element ⁇ may be a multi layered structure formed of a Cu film 17 and a Mn film 18 , as in the fourth embodiment. Also in this modification, a heat treatment for diffusing Mn is performed after forming the upper insulating film 20 containing oxygen, so that the same effects can be obtained.
  • an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO 2 .
  • an alloy film 13 made of Cu and Mn (auxiliary film containing a predetermined metal element ⁇ ) is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12 .
  • the alloy film 13 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm.
  • the Mn content in the alloy film 13 is set to be 0.05 to 20 at % (atomic percentage).
  • a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a .
  • the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12 .
  • a heat treatment is performed on the structure shown in FIG. 9B , at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
  • the heat treatment is performed within an atmosphere containing oxygen, such as an inactive gas atmosphere of, e.g., Ar, containing O 2 at a volume ratio of 1 ppm to 10%.
  • Mn in the alloy film 13 is supplied with a force in directions to remove it from Cu, and thereby diffuses onto the surface of the interlevel insulating film 11 facing the alloy film 13 , and also diffuses to the upper surface of the Cu layer 16 a .
  • Mn thus supplied from the alloy film 13 reacts with O used as a component element of the interlevel insulating film 11 , and with O present within the heat treatment atmosphere.
  • a barrier film 14 containing MnO as the main component is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11 , and have a thickness of 5 nm or less, e.g., 2 nm.
  • an upper barrier film 14 a containing MnO as the main component is also formed to cover the upper surface of the Cu layer 16 a .
  • the upper barrier film can be used as a film for preventing Cu from diffusing from the Cu layer 16 a into an interlevel insulating film further formed thereon.
  • the auxiliary film containing a predetermined metal element ⁇ may be a multi layered structure formed of a Cu film 17 and a Mn film 18 , as in the fourth embodiment. Also in this modification, a heat treatment for diffusing Mn is performed within an atmosphere containing oxygen after CMP, so that the same effects can be obtained.
  • an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO 2 .
  • an alloy film 13 made of Cu and Mn (auxiliary film containing a predetermined metal element ⁇ ) is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12 .
  • the alloy film 13 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm.
  • the Mn content in the alloy film 13 is set to be 0.05 to 20 at % (atomic percentage).
  • a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a .
  • the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12 .
  • an upper insulating film 20 containing oxygen such as a SiO 2 film, or SiC, SiCN, or SiN film containing oxygen, is formed on the upper surface of the Cu layer 16 a .
  • a heat treatment is performed on the structure shown in FIG. 10B , at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
  • Mn in the alloy film 13 is supplied with a force in directions to remove it from Cu, and thereby diffuses onto the surface of the interlevel insulating film 11 facing the alloy film 13 , and also diffuses to the upper surface of the Cu layer 16 a .
  • Mn thus supplied from the alloy film 13 reacts with O used as a component element of the interlevel insulating film 11 , and with O used as a component element of the upper insulating film 20 .
  • a barrier film 14 containing MnO as the main component is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11 , and have a thickness of 5 nm or less, e.g., 2 nm.
  • an upper barrier film 14 a containing MnO as the main component is also formed to cover the upper surface of the Cu layer 16 a.
  • the auxiliary film containing a predetermined metal element ⁇ may be a multi layered structure formed of a Cu film 17 and a Mn film 18 , as in the fourth embodiment. Also in this modification, a heat treatment for diffusing Mn is performed after performing CMP and then forming the upper insulating film 20 containing oxygen, so that the same effects can be obtained.
  • an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO 2 .
  • a Cu film 17 is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12 .
  • the Cu film 17 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm.
  • the Cu film 17 works as a seed layer for forming a Cu main film by electrolytic plating described later.
  • a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a .
  • a Mn film (auxiliary film containing a predetermined metal element ⁇ ) 18 is formed on the Cu main film 16 .
  • the Mn film 18 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm.
  • a heat treatment is performed on the structure shown in FIG. 11B , at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
  • Mn in the Mn film 18 diffuses onto the surface of the interlevel insulating film 11 facing the Cu film 17 .
  • Mn thus supplied from the Mn film 18 reacts with O used as a component element of the interlevel insulating film 11 .
  • a barrier film 14 containing, as the main component, a very stable compound or oxide made of MnO is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11 , and have a thickness of 5 nm or less, e.g., 2 nm.
  • the Cu film 17 is essentially integrated with the interconnection main layer formed of the Cu layer 16 a.
  • the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12 .
  • an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO 2 .
  • a Cu film 17 is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12 .
  • the Cu film 17 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm.
  • a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a .
  • a Mn film (auxiliary film containing a predetermined metal element ⁇ ) 18 is formed on the Cu main film 16 .
  • the Mn film 18 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm.
  • a heat treatment is performed on the structure shown in FIG. 12B , at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes. At this time, the heat treatment is performed within an atmosphere containing oxygen, such as an inactive gas atmosphere of, e.g., Ar, containing O 2 at a volume ratio of 1 ppm to 10%.
  • Mn in the Mn film 18 diffuses onto the surface of the interlevel insulating film 11 facing the Cu film 17 , and also stays at the upper surface of the Cu main film 16 due to an influence of oxygen contained in the heat treatment atmosphere. Mn thus supplied from the Mn film 18 reacts with O used as a component element of the interlevel insulating film 11 , and with O present within the heat treatment atmosphere.
  • a barrier film 14 containing MnO as the main component is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11 , and have a thickness of 5 nm or less, e.g., 2 nm.
  • an insulating film (reaction product film) 19 containing MnO as the main component is also formed to cover the upper surface of the Cu main film 16 .
  • the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed along with the insulating film 19 by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12 .
  • an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO 2 .
  • a Cu film 17 is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12 .
  • the Cu film 17 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm.
  • a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a .
  • a Mn film (auxiliary film containing a predetermined metal element ⁇ ) 18 is formed on the Cu main film 16 .
  • the Mn film 18 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm.
  • a heat treatment is performed on the structure shown in FIG. 13B , at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
  • Mn in the Mn film 18 diffuses onto the surface of the interlevel insulating film 11 facing the alloy film 13 , and also stays at the upper surface of the Cu main film 16 due to an influence of oxygen contained in the upper insulating film 20 as a component element.
  • Mn thus supplied from the Mn film 18 reacts with O used as a component element of the interlevel insulating film 11 , and with O used as a component element of the upper insulating film 20 .
  • a barrier film 14 containing MnO as the main component is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11 , and have a thickness of 5 nm or less, e.g., 2 nm.
  • an insulating film (reaction product film) 19 containing MnO as the main component is also formed to cover the upper surface of the Cu main film 16 .
  • the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed along with the insulating film 19 and upper insulating film 20 by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12 .
  • FIG. 14 is a view showing characteristics of various Cu alloys, in terms of change in resistivity relative to heat treatment temperature.
  • the horizontal axis denotes heat treatment temperature T(° C.)
  • the vertical axis denotes alloy resistivity R ( ⁇ cm).
  • the resistivity greatly increases when the heat treatment temperature exceeds 350° C.
  • the resistivity decreases to be equal to that of pure copper as the heat treatment temperature is higher.
  • Mn used as the alloy element does not stay as solid solution in the Cu film, but moves to the interface, thereby reducing the resistivity to be equal to that of pure copper. Accordingly, Mn used as the alloy element can realize an interconnection with a lower resistance, as compared to conventional interconnections.
  • FIG. 15 is a view showing a TEM micrographic image of a cross section of a semiconductor device manufactured by the first embodiment.
  • a stable compound is formed at the interface between the Cu layer 16 a and interlevel insulating film 11 .
  • an alloy film of Cu with Mn is employed and formed as an auxiliary film containing Mn or a predetermined metal element ⁇ , and is then subjected to a heat treatment.
  • a MnO barrier film is formed by means of self alignment at the interface between the alloy film and the interlevel insulating film or SiO 2 film.
  • the resistivity of the portion where the alloy film was formed becomes as low as pure copper, after the heat treatment.
  • a Cu interconnection is formed by a barrier self formation process without increasing the electric resistance of the interconnection, thereby improving the reliability of the interconnection structure and reducing the interconnection resistance.
  • the same effects can be also attained in any one of the second to thirteenth embodiments described above.
  • the methods described above according to the first to thirteenth embodiments are preferably applicable to a damascene interconnection structure, as shown in the following embodiments.
  • FIGS. 16A to 16F are sectional views showing sequential steps of a semiconductor device manufacturing method according to a fourteenth embodiment of the present invention.
  • the first embodiment is applied to a dual damascene interconnection structure.
  • an interlevel insulating film 31 formed of, e.g., a SiO 2 film is disposed with an interconnection groove formed in the surface thereof, on a semiconductor substrate Sub.
  • the interconnection groove is filled with a Cu layer (lower interconnection layer (i.e., conductive layer)) 33 with a barrier film 32 interposed therebetween.
  • the barrier film 32 and Cu layer 33 may be prepared by a method according to any one of the first to thirteenth embodiments.
  • a diffusion prevention film (lower insulating film) 34 such as SiN or SiCN, is formed.
  • an interlevel insulating film 41 made of SiO 2 is deposited to have a thickness of 150 to 600 nm.
  • an opening 42 is formed in the interlevel insulating film 41 to include an interconnection hole 42 a for connection to the Cu layer 33 and an interconnection groove 42 b.
  • an alloy film 43 made of Cu and Mn (auxiliary film containing a predetermined metal element ⁇ ) is formed by, e.g., CVD to cover the inner surface of the opening 42 and have a thickness of 5 to 100 nm.
  • a heat treatment is performed at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
  • a barrier film 44 containing MnO as the main component is formed to cover the inner surface of the opening 42 of the interlevel insulating film 41 .
  • no barrier film 44 is formed, but only a Cu film 45 is formed. Accordingly, a Cu upper interconnection layer formed later will come into essentially direct contact with the Cu layer (lower interconnection layer) 33 with no barrier film 44 interposed therebetween.
  • a Cu main film 46 having a thickness of 0.8 to 1 ⁇ m is deposited all over by electrolytic plating to fill the opening 42 with the Cu main film (upper interconnection layer) 46 .
  • the unnecessary portion of the Cu main film 46 is removed by CMP to planarize the structure surface.
  • a diffusion prevention film 49 such as a SiC, SiCN, or SiN film, is formed all over the structure surface.
  • the alloy film 43 may be formed by any one of PVD, CVD, and electroless plating methods.
  • a source gas containing Mn is employed.
  • a plating solution containing Mn is employed.
  • the Cu Mn alloy film 43 preferably contains 0.05 to 20% Mn by atomic percentage.
  • the heat treatment for diffusing Mn to the surface of the interlevel insulating film 41 is preferably performed at a temperature of 50 to 400° C. for 60 minutes or less.
  • the barrier film 44 containing MnO as the main component is formed by means of self alignment at the interface between the Cu main film 46 used as an interconnection main layer and the SiO 2 interlevel insulating film 41 .
  • the Cu main film 46 used as an upper interconnection layer is in essentially direct contact with the Cu lower interconnection layer 33 with no barrier film interposed therebetween, and the contact resistance between the interconnection layers is thereby reduced.
  • a Cu interconnection is formed by barrier self formation process without increasing the electric resistance of the interconnection, thereby improving the reliability of the interconnection structure and reducing the interconnection resistance.
  • FIG. 17 is a sectional view showing a semiconductor device according to a modification of the fourteenth embodiment.
  • an interconnection hole 42 a may partly deviate from the lower interconnection layer 33 .
  • a barrier film 44 is formed on an interlevel insulating film 31 even to the bottom of the interconnection hole 42 a , and thus a part of the barrier film 44 is present at the bottom of the opening 42 .
  • no barrier film 44 is formed between the upper and lower interconnection layers 46 and 33 . Accordingly, unless the positional deviation is excessively large, the upper and lower interconnection layers 46 and 33 have sufficient contact therebetween.
  • FIG. 18 is a sectional view showing a semiconductor device according to a fifteenth embodiment of the present invention.
  • the first embodiment is applied to a single damascene interconnection structure.
  • This device may be manufactured by a method almost the same as that of the fourteenth embodiment, except for the following points.
  • an interlevel insulating film 51 made of SiO 2 and having a thickness of 150 to 300 nm is deposited, and an interconnection hole 52 for connection to a lower interconnection layer 33 is formed therein.
  • a Cu Mn alloy film is formed by, e.g., CVD to cover the inner surface of the interconnection hole 52 and have a thickness of 5 to 100 nm.
  • a heat treatment is performed to form a MnO barrier film 54 on the inner surface of the hole of the interlevel insulating film 51 .
  • a Cu film 56 is formed to fill the interconnection hole 52 , and the unnecessary portion of the Cu film 56 is removed by CMP.
  • an interlevel insulating film 61 , an interconnection groove 62 , a MnO barrier film 64 , and a Cu film 66 are formed by the same processes used for the parts 51 to 56 . Then, the unnecessary portion of the Cu film 66 is removed by CMP, and a diffusion prevention film 49 is formed.
  • the MnO barrier films 54 and 64 are formed between the Cu films 56 and 66 filling the interconnection hole 52 and interconnection groove 62 , and the interlevel insulating films 51 and 61 .
  • the Cu film 56 used as a connection plug is in direct contact with the Cu lower interconnection layer 33
  • the Cu film 66 used as an upper interconnection layer is in direct contact with the Cu film 56 .
  • FIGS. 19A to 19C are sectional views showing sequential steps of a semiconductor device manufacturing method according to a sixteenth embodiment of the present invention.
  • the tenth embodiment is applied to a dual damascene interconnection structure.
  • a Cu main film 46 is formed to fill the opening 42 , as shown in FIG. 19A .
  • the unnecessary portion of the Cu main film 46 is removed by CMP to planarize the surface.
  • an upper insulating film 79 containing oxygen, such as a SiO 2 film, is formed on the upper surface of the Cu main film 46 .
  • a heat treatment is performed on the structure shown in FIG. 19A , at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
  • a barrier film 44 containing MnO as the main component is formed to cover the inner surface of the opening 42 of the interlevel insulating film 41 .
  • no barrier film 44 is formed at the bottom of the interconnection hole 42 a .
  • the upper and lower interconnection layers 46 and 33 are in essentially direct contact with each other with no barrier film 44 interposed therebetween.
  • the oxide film 79 is present on the upper surface of the Cu main film 46 , Mn diffuses there, thereby forming an upper barrier film (reaction product film) 47 containing MnO as the main component.
  • the upper insulating film 79 is removed. As a consequence, only the upper barrier film 47 functioning as a barrier film is left on the Cu main film 46 (no barrier film 47 is present above the interlevel insulating film 41 ).
  • this embodiment can provide the following effects because of the upper barrier film 47 present only on the Cu main film 46 .
  • a Cu embedded interconnection structure requires a diffusion prevention film with a high dielectric constant, such as a SiC, SiCN, or SiN film, to be disposed on the Cu main film 46 .
  • a diffusion prevention film is disposed all over the structure surface, the capacitance between adjacent interconnections becomes higher due to the presence of the diffusion prevention film.
  • the barrier film 47 disposed on the Cu main film 46 functions as a protection film, and thus requires no additional diffusion prevention film to be formed. Accordingly, there is no high dielectric constant film, such as a nitride film, present between adjacent interconnections, thereby reducing the capacitance between the adjacent interconnections.
  • FIGS. 20A to 20E are sectional views showing sequential steps of a semiconductor device manufacturing method according to a seventeenth embodiment of the present invention.
  • the seventh embodiment is applied to a dual damascene interconnection structure.
  • an interlevel insulating film 81 formed of, e.g., a SiO 2 film is disposed with an interconnection groove formed in the surface thereof, on a semiconductor substrate Sub.
  • the interconnection groove is filled with a Cu layer (lower interconnection layer (i.e., conductive layer)) 83 with a barrier film 82 interposed therebetween.
  • the barrier film 82 and Cu layer 83 may be prepared by a method according to any one of the first to thirteenth embodiments.
  • a diffusion prevention film (lower insulating film) 84 is formed.
  • the diffusion prevention film 84 is made of, e.g., SiN or SiCN containing oxygen at a concentration of 33% or less by atomic percentage, and having an atomic density higher than the interlevel insulating film 81 .
  • an interlevel insulating film 91 made of SiO 2 is deposited to have a thickness of 150 to 600 nm.
  • an opening 92 is formed in the interlevel insulating film 91 to include an interconnection hole 92 a for connection to the Cu layer (lower interconnection layer) 83 and an interconnection groove 92 b .
  • the interconnection hole 92 a is formed to pass through the diffusion prevention film 84 and reach the lower interconnection layer 83 .
  • an alloy film 93 made of Cu and Mn (auxiliary film containing a predetermined metal element ⁇ ) is formed by, e.g., CVD to cover the inner surface of the opening 92 and have a thickness of 5 to 100 nm.
  • a Cu main film 96 having a thickness of 0.8 to 1 ⁇ m is deposited all over by electrolytic plating to fill the opening 92 with the Cu main film (upper interconnection layer) 96 .
  • a heat treatment is performed on the structure shown in FIG. 20C , at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes. At this time, the heat treatment is performed within an atmosphere containing oxygen, such as an inactive gas atmosphere of, e.g., Ar, containing O 2 at a volume ratio of 1 ppm to 10%.
  • a barrier film 94 containing MnO as the main component is formed to cover the inner surface of the opening 92 of the interlevel insulating film 91 . Further, since the upper surface of the Cu main film 96 is exposed to the atmosphere containing oxygen, Mn diffuses there, thereby forming an insulating film (reaction product film) 97 containing MnO as the main component.
  • the unnecessary portion of the Cu main film 96 is removed along with the insulating film 97 by CMP to planarize the structure surface.
  • a diffusion prevention film 99 such as a SiN or SiCN film, is formed all over the structure surface.
  • the diffusion prevention film 84 interposed between the lower interconnection layer 83 and interlevel insulating film 91 contains oxygen.
  • the barrier film 94 containing MnO as the main component is reliably formed by means of self alignment also on the inner surface of the portion 92 s of the interconnection hole 92 a passing through the diffusion prevention film 84 . This can prevent defects from being generated in the barrier film 94 at this portion 92 s , which would allow Cu to diffuse through from the interconnection layer.
  • FIG. 21 is a graph showing the oxygen concentration distribution in the diffusion prevention film 84 according to a modification of the seventeenth embodiment.
  • the horizontal axis denotes the position Th (nm) of the diffusion prevention film 84 in the film thickness direction, relative to the surface of the lower interconnection layer 83 used as the reference point, and the vertical axis denotes the oxygen concentration Con O (atomic %) in the diffusion prevention film 84 .
  • the oxygen concentration in the diffusion prevention film 84 is high near the lower interconnection layer 83 , Cu in the lower interconnection layer 83 may be oxidized, thereby deteriorating device properties. For this reason, in this modification, the oxygen concentration in the diffusion prevention film 84 is set lower on the lower interconnection layer 83 side than on the interlevel insulating film 91 side.
  • a method of depositing the film 84 by CVD may be arranged such that the oxygen concentration in the process atmosphere is set lower at first, and is then gradually increased.
  • the diffusion prevention film 84 may have a multi layered structure formed of a lower layer of several nm and an upper layer both deposited by CVD, in which only the lower layer has a lower oxygen concentration, while the upper layer has a sufficiently high oxygen concentration.
  • FIGS. 22A to 22E are sectional views showing sequential steps of a semiconductor device manufacturing method according to an eighteenth embodiment of the present invention. This embodiment is a modification of the seventeenth embodiment.
  • an interlevel insulating film 81 is disposed with an interconnection groove formed in the surface thereof, on a semiconductor substrate Sub.
  • the interconnection groove is filled with a Cu layer (lower interconnection layer) 83 with a barrier film 82 interposed therebetween.
  • the barrier film 82 and Cu layer 83 may be prepared by a method according to any one of the first to thirteenth embodiments.
  • a refractory metal layer 104 is formed on the barrier film 82 and Cu layer 83 .
  • the refractory metal layer 104 is made of, e.g., CoW, CoWB, CoWP, or CuSi to prevent the lower interconnection layer 83 from being oxidized or causing Cu diffusion.
  • an interlevel insulating film 111 made of SiO 2 is deposited to have a thickness of 150 to 600 nm.
  • an opening 112 is formed in the interlevel insulating film 111 to include an interconnection hole 112 a for connection to the Cu layer 83 and an interconnection groove 112 b .
  • the interconnection hole 112 a is formed to terminate on the upper surface of the refractory metal layer 104 .
  • an alloy film 113 made of Cu and Mn (auxiliary film containing a predetermined metal element ⁇ ) is formed by, e.g., CVD to cover the inner surface of the opening 112 and have a thickness of 5 to 100 nm.
  • a Cu main film 116 having a thickness of 0.8 to 1 ⁇ m is deposited all over by electrolytic plating to fill the opening 112 with the Cu main film (upper interconnection layer) 116 .
  • a heat treatment is performed on the structure shown in FIG. 22C , at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes. At this time, the heat treatment is performed within an atmosphere containing oxygen, such as an inactive gas atmosphere of, e.g., Ar, containing O 2 at a volume ratio of 1 ppm to 10%.
  • a barrier film 114 containing MnO as the main component is formed to cover the inner surface of the opening 112 of the interlevel insulating film 111 . Further, since the upper surface of the Cu main film 116 is exposed to the atmosphere containing oxygen, Mn diffuses there, thereby forming an insulating film (reaction product film) 117 containing MnO as the main component.
  • a diffusion prevention film 119 such as a SiN or SiCN film, is formed all over the structure surface.
  • the lower interconnection layer 83 since the upper surface of the lower interconnection layer 83 is covered with the refractory metal layer 104 , the lower interconnection layer 83 is prevented from being oxidized or causing Cu diffusion.
  • FIG. 23 is a sectional view showing a semiconductor device according to a modification of the eighteenth embodiment.
  • an interconnection hole 112 a formed in the interlevel insulating film 111 further passes through the refractory metal layer 104 and reaches the lower interconnection layer 83 .
  • the upper and lower interconnection layers 116 and 83 are in direct contact with each other, thereby reducing the interconnection resistance.
  • FIGS. 24A to 24F are sectional views showing sequential steps of a semiconductor device manufacturing method according to a nineteenth embodiment of the present invention. This embodiment is another modification of the seventeenth embodiment.
  • an interlevel insulating film 121 is disposed with an interconnection groove formed in the surface thereof, on a semiconductor substrate Sub.
  • the interlevel insulating film 121 is formed of a low dielectric constant film, such as a porous SiO 2 , SiC, SiOC, SiOCH, or SiCOF film.
  • the interconnection groove is filled with a Cu layer (lower interconnection layer (i.e., conductive layer)) 123 with a barrier film 122 interposed therebetween.
  • the barrier film 122 and Cu layer 123 may be prepared by a method according to any one of the first to thirteenth embodiments.
  • a diffusion prevention film (lower insulating film) 124 is formed in this order.
  • the diffusion prevention film 124 is made of, e.g., SiN or SiCN having an atomic density higher than the interlevel insulating film 121 , but containing essentially no oxygen unlike the diffusion prevention film 84 describe above.
  • the interlevel insulating film 125 consists of a porous low dielectric constant film, essentially the same as that used for the interlevel insulating film 121 .
  • the etching stop film 126 is made of an insulating material, such as SiN, SiCN, or polymer material, e.g., PAE (polyallylene), which contains oxygen at a concentration of 33% or less by atomic percentage, and has an atomic density higher than the interlevel insulating films 121 and 125 .
  • an insulating material such as SiN, SiCN, or polymer material, e.g., PAE (polyallylene), which contains oxygen at a concentration of 33% or less by atomic percentage, and has an atomic density higher than the interlevel insulating films 121 and 125 .
  • an interlevel insulating film 127 consisting of a porous low dielectric constant film, the same as that used for the interlevel insulating film 121 , is formed on the etching stop film 126 .
  • an opening 132 is formed in the interlevel insulating film 127 and diffusion prevention film 124 to include an interconnection hole 132 a for connection to the Cu layer (lower interconnection layer) 123 and an interconnection groove 132 b .
  • the interconnection groove 132 b is formed to terminate on the etching stop film 126
  • the interconnection hole 132 a is formed to extend therefrom through the diffusion prevention film 124 onto the lower interconnection layer 123 .
  • a coating film 128 which is made of an insulating material containing oxygen and having a higher atomic density, i.e., the same material as the etching stop film 126 , is formed to cover the inner surface of the opening 132 .
  • anisotropic etching is performed vertically from above by RIE, to remove the portion of the coating film 128 at the bottom of the interconnection hole 132 a , so that the lower interconnection layer 123 is exposed.
  • the portion of the coating film 128 on the etching stop film 126 is also removed, and the etching stop film 126 is thereby exposed.
  • an alloy film 133 made of Cu and Mn (auxiliary film containing a predetermined metal element ⁇ ) is formed by, e.g., CVD to cover the inner surface of the opening 132 (surfaces of the etching stop film 126 and coating film 128 ) and have a thickness of 5 to 100 nm.
  • a Cu main film 136 having a thickness of 0.8 to 1 ⁇ m is deposited all over by electrolytic plating to fill the opening 132 with the Cu main film (upper interconnection layer) 136 .
  • a heat treatment is performed on the structure shown in FIG. 24D , at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes. At this time, the heat treatment is performed within an atmosphere containing oxygen, such as an inactive gas atmosphere of, e.g., Ar, containing O 2 at a volume ratio of 1 ppm to 10%.
  • a barrier film 134 containing MnO as the main component is formed to cover the inner surface of the opening 132 of the interlevel insulating films 125 and 127 . Further, since the upper surface of the Cu main film 136 is exposed to the atmosphere containing oxygen, Mn diffuses there, thereby forming an insulating film (reaction product film) 137 containing MnO as the main component.
  • a diffusion prevention film 139 such as a SiN or SiCN film, is formed all over the structure surface.
  • the barrier film 134 containing MnO as the main component is formed while using oxygen present within the etching stop film 126 and coating film 128 , which cover the interlevel insulating films 125 and 127 .
  • porous low dielectric constant films are used as the interlevel insulating films 125 and 127 to improve the operation speed of the device.
  • the embodiment described above is exemplified by a case where Cu is used as the material of the interconnection main layer.
  • the interconnection main layer may be made of another material containing Cu as the main component (i.e., by 50% or more), such as a Cu alloy commonly used as an interconnection material. Also in such a case, the same effects as described above can be attained.
  • the metal element ⁇ is not limited to Mn, and it may comprise at least one element selected from the group consisting of Mn, Nb, Zr, Cr, V, Y, Tc, and Re.
  • These metal elements have the following advantages, as compared to Ti and Ta, which are used for conventional barrier films, and Al, Mg, and Sn, which have been proposed by conventional barrier less process techniques.
  • the metal elements listed above for the metal element ⁇ can easily form an oxide and the oxide is high in affinity with interlevel insulating films. Accordingly, they can provide a stable oxide layer with uniform quality and very small thickness between an interconnection main layer and an interlevel insulating film. Further, since these elements tend to precipitate or form a compound, rather than staying as solid solution in Cu, they do not increase the interconnection resistance.
  • interlevel insulating films are not limited to SiO 2 , and various insulating films may be used.
  • an interlevel insulating film contains a SiO bond group as the main component, such as SiO 2 , it forms ⁇ x O y or ⁇ x Si y O z by reaction with the metal element ⁇ .
  • an interlevel insulating film contains an organic component, such as CC, it forms a compound containing this component element by reaction with the metal element ⁇ . In this latter case, the compound can function as a layer like MnO for preventing Cu diffusion, and provide the same effects as described above.
  • a method of filling or embedding the Cu film is not limited to a method utilizing electrolytic plating, and it may be a method utilizing CVD, PVD, electroless plating, or film formation using critical liquid.
  • the same effects as described above can be attained by any method, as long as it can embed Cu within a groove and/or a hole formed in an insulating film.
  • the embodiments described above may be applied to any one of the interconnections from the lowermost level to the uppermost level in a multi layered interconnection structure disposed on a semiconductor substrate.
  • the fourteenth to nineteenth embodiments are exemplified by application to the second level interconnection, but may also be applied to the first level interconnection in the same way.
  • FIG. 25 is a sectional view showing a semiconductor device according to a modification of the fourteenth embodiment.
  • a first level interconnection structure is formed by a method according to the fourteenth embodiment.
  • the first level interconnection structure has a dual damascene interconnection structure, which includes an interlevel insulating film 41 1 , a Cu layer 46 1 , a MnO barrier film 44 1 , and a diffusion prevention film 49 1 .
  • a second level interconnection structure is formed by a method according to the fourteenth embodiment.
  • the second level interconnection structure has a dual damascene interconnection structure, which includes an interlevel insulating film 41 2 , a Cu layer 46 2 , a MnO barrier film 44 2 , and a diffusion prevention film 49 2 .
  • a multi layered interconnection structure as shown in FIG. 25 , may be manufactured in the same manner, using any of the other embodiments. If necessary, different embodiments selected from the first to thirteenth embodiments may be respectively applied to different level interconnection structures.
  • the fourteenth to nineteenth embodiments are exemplified by a case where a dual damascene or single damascene interconnection structure is used.
  • the present invention may be applied to various embedded interconnection structures other than damascene interconnection structures.

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Abstract

A method of manufacturing a semiconductor device, including forming an opening in an interlevel insulating film disposed on a semiconductor substrate, forming an auxiliary film containing a predetermined metal element, to cover an inner surface of the opening, forming a main film to fill the opening after forming the auxiliary film, the main film containing, as a main component, Cu used as a material of an interconnection main layer, and performing a heat treatment before or after forming the main film, thereby diffusing the predetermined metal element of the auxiliary film onto a surface of the interlevel insulating film facing the auxiliary film, so as to form a barrier film on the interlevel insulating film within the opening, the barrier film containing, as a main component, a compound of the predetermined metal element with a component element of the interlevel insulating film.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a divisional application of U.S. application Ser. No. 11/063,876, filed Feb. 24, 2005 and is based upon and claims the benefit of priority from prior Japanese Patent Applications No. 2004-053458, filed Feb. 27, 2004; and No. 2005-027756, filed Feb. 3, 2005, the entire contents of both of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a semiconductor device including an interconnection, which has an interconnection main layer containing Cu (copper) as the main component (i.e., by 50% or more), wherein such an interconnection will be also referred to as a Cu interconnection, for the sake of convenience. The present invention also relates to a semiconductor device manufacturing method for forming such an interconnection by a barrier self-formation process. Particularly, the present invention relates to a semiconductor device and manufacturing method thereof, utilizing a damascene interconnection structure.
2. Description of the Related Art
In recent years, interconnection structures employing Cu and an insulating film with a low dielectric constant have been developed to increase the speed and integration degree of silicon (Si) semiconductor integrated circuits. Where a Cu interconnection structure is used for an integrated circuit, the Cu interconnection easily causes counter diffusion relative to an insulating layer around it, or easily causes a reaction in an oxygen atmosphere and produces a Cu oxide film, during various heat treatments used for manufacturing the integrated circuit. In order to prevent these problems, it is necessary to form a diffusion barrier film, such as a tantalum (Ta) or tantalum nitride (TaN) film, before the Cu layer (interconnection main layer) is formed. Particularly, where an embedded Cu layer is formed in an interlevel insulating film, as in a damascene interconnection structure, Cu diffusion into the insulating film becomes prominent, and thus a diffusion barrier film is indispensable.
In order to ensure that Cu interconnection structures are reliable, they need to have a barrier film with a thickness of 10 nm or more, under the present process technique. However, barrier films are required to be thinner with generation changes to reduce the interconnection resistance, because the interconnection width will decrease, thereby increasing the resistance. In this respect, conventional barrier film formation methods entail some difficulties in depositing a barrier film on the side surface of an interconnection groove or via hole (interconnection hole) with uniform thickness and quality. As a consequence, it is difficult to ensure a required barrier property level of the barrier film, the adhesiveness at the interface between the barrier film and Cu layer, and the resistance against electromigration due to interface diffusion, thereby causing problems in reliability.
As an ultimate arrangement to solve these problems while reducing the thickness of the barrier film, a barrier less structure, which does not include any conventional barrier film formation process, is conceivable. It has been proposed, as a method of forming a barrier less structure, to add an alloy element in a Cu layer and perform a heat treatment on the Cu layer, so as to diffuse the alloy element to the interface between the Cu layer and an insulating layer, at which the alloy element reacts with the insulating layer and thereby forms a stable compound.
Major elements reported so far to be usable as the alloy element described above are Al, Mg, and Sn. However, these elements greatly increase the electric resistance, while there is no report saying that they form a stable compound at the interface. Accordingly, under the present circumstances, a barrier less structure is expected as an ultimate interconnection structure, but is considered to be very difficult to achieve. In this respect, although a barrier less structure was included in loadstars for the future on the roadmap of ITRS (International Technology Roadmap for Semiconductor) in 1999, it was excluded therefrom in 2001.
As described above, conventionally, where an interconnection structure employs a Cu interconnection formed in an interlevel insulating film, a barrier film is required to ensure the reliability of the structure. However, the presence of the barrier film brings about problems, such as an increase in interconnection resistance, and a decrease in interconnection reliability. On the other hand, although a barrier less structure is expected as an ultimate interconnection structure, such a structure is very difficult to achieve. Accordingly, it is desired to provide a semiconductor device and manufacturing method thereof which can improve the reliability of an interconnection structure and decrease the interconnection resistance.
The following publications disclose techniques relating to the present invention:
[Patent Publication 1]
Jpn. Pat. Appln. KOKAI Publication No. 2 62035
[Non Patent Publication 1]
W. A. Lanford et al., Thin Solid Films, 262 (1995) 234 241
BRIEF SUMMARY OF THE INVENTION
According to a first aspect of the present invention, there is provided a semiconductor device comprising:
an interlevel insulating film disposed on a semiconductor substrate and having an opening formed therein;
an interconnection main layer embedded in the opening and containing Cu as a main component; and
a barrier film interposed between the interlevel insulating film and the interconnection main layer within the opening, the barrier film containing, as a main component, a compound of a predetermined metal element with a component element of the interlevel insulating film.
According to a second aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising:
forming an opening in an interlevel insulating film disposed on a semiconductor substrate;
forming an auxiliary film containing a predetermined metal element, to cover an inner surface of the opening;
forming a main film to fill the opening after forming the auxiliary film, the main film containing, as a main component, Cu used as a material of an interconnection main layer; and
performing a heat treatment before or after forming the main film, thereby diffusing the predetermined metal element of the auxiliary film onto a surface of the interlevel insulating film facing the auxiliary film, so as to form a barrier film on the interlevel insulating film within the opening, the barrier film containing, as a main component, a compound of the predetermined metal element with a component element of the interlevel insulating film.
According to a third aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising:
forming an opening in an interlevel insulating film disposed on a semiconductor substrate;
forming a main film to fill the opening, the main film containing, as a main component, Cu used as a material of an interconnection main layer;
forming an auxiliary film containing a predetermined metal element on the main film after forming the main film; and
performing a heat treatment after forming the auxiliary film, thereby diffusing the predetermined metal element of the auxiliary film onto a surface of the interlevel insulating film facing the main film, so as to form a barrier film on the interlevel insulating film within the opening, the barrier film containing, as a main component, a compound of the predetermined metal element with a component element of the interlevel insulating film.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
FIGS. 1A to 1C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a first embodiment of the present invention;
FIGS. 2A to 2C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a second embodiment of the present invention;
FIGS. 3A to 3C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a third embodiment of the present invention;
FIGS. 4A to 4C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a fourth embodiment of the present invention;
FIGS. 5A to 5C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a fifth embodiment of the present invention;
FIGS. 6A to 6C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a sixth embodiment of the present invention;
FIGS. 7A to 7C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a seventh embodiment of the present invention;
FIGS. 8A to 8C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to an eighth embodiment of the present invention;
FIGS. 9A to 9C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a ninth embodiment of the present invention;
FIGS. 10A to 10C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a tenth embodiment of the present invention;
FIGS. 11A to 11C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to an eleventh embodiment of the present invention;
FIGS. 12A to 12C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a twelfth embodiment of the present invention;
FIGS. 13A to 13C are sectional views showing the basic arrangement of sequential steps of a semiconductor device manufacturing method according to a thirteenth embodiment of the present invention;
FIG. 14 is a view showing characteristics of various Cu alloys, in terms of change in resistivity relative to heat treatment temperature;
FIG. 15 is a view showing a TEM micrographic image of a cross section of a semiconductor device manufactured by the first embodiment;
FIGS. 16A to 16F are sectional views showing sequential steps of a semiconductor device manufacturing method according to a fourteenth embodiment of the present invention;
FIG. 17 is a sectional view showing a semiconductor device according to a modification of the fourteenth embodiment;
FIG. 18 is a sectional view showing a semiconductor device according to a fifteenth embodiment of the present invention;
FIGS. 19A to 19C are sectional views showing sequential steps of a semiconductor device manufacturing method according to a sixteenth embodiment of the present invention;
FIGS. 20A to 20E are sectional views showing sequential steps of a semiconductor device manufacturing method according to a seventeenth embodiment of the present invention;
FIG. 21 is a graph showing the oxygen concentration distribution in a diffusion prevention film according to a modification of the seventeenth embodiment;
FIGS. 22A to 22E are sectional views showing sequential steps of a semiconductor device manufacturing method according to an eighteenth embodiment of the present invention;
FIG. 23 is a sectional view showing a semiconductor device according to a modification of the eighteenth embodiment;
FIGS. 24A to 24F are sectional views showing sequential steps of a semiconductor device manufacturing method according to a nineteenth embodiment of the present invention; and
FIG. 25 is a sectional view showing a semiconductor device according to a modification of the fourteenth embodiment.
 DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will now be described with reference to the accompanying drawings. In the following description, the constituent elements having substantially the same function and arrangement are denoted by the same reference numerals, and a repetitive description will be made only when necessary.
According to the following embodiments of the present invention, a barrier film for preventing Cu diffusion is formed by means of self alignment between an interconnection main layer containing Cu as the main component (i.e., by 50% or more) and an interlevel insulating film. This barrier film contains a compound of a predetermined metal element α with a component element of the interlevel insulating film. The predetermined metal element α may comprise at least one element selected from the group consisting of Mn, Nb, Zr, Cr, V, Y, Tc, and Re, and preferably comprise Mn.
The metal elements listed above to be usable as the predetermined metal element α have the following advantages, as compared to Ti and Ta, which are used for conventional barrier films, and Al, Mg, and Sn, which have been proposed by conventional barrier less process techniques. Specifically, the metal elements listed above for the metal element α can easily form an oxide and the oxide is high in affinity with interlevel insulating films. Accordingly, they can provide a stable oxide layer with uniform quality and very small thickness between an interconnection main layer and an interlevel insulating film. Further, since these elements tend to precipitate or form a compound, rather than staying as solid solution in Cu, they do not increase the interconnection resistance.
The interlevel insulating film may comprise O and at least one element selected from the group consisting of Si, C, and F. More specifically, the interlevel insulating film may be made of SiO2, SiOxCy, SiOxCyHz, or SiOxFy. The barrier film may contain, as the main component, a material selected from the group consisting of αxOy, αxSiyOz, αxCyOz, and αxFyOz, where α denotes the predetermined metal element α described above.
A set of FIGS. 1A to 1C to a set of FIGS. 13A to 11 respectively show semiconductor device manufacturing methods according to different embodiments of the present invention, by sectional views showing the basic arrangement of sequential steps thereof. For the sake of simplicity, the following explanation on these embodiments will be given such that the material of an interconnection main layer is Cu, the metal element α for a barrier film is Mn, and the material of the barrier film is MnO. The composition of the barrier film is simply referred to as MnO in consideration of the function of preventing Cu diffusion and for the sake of convenience, although it can be expressed more properly by MnxSiyOz (x:y:z=1:1:3 to 1:3:5), as shown in FIG. 15.
First Embodiment
As shown in FIG. 1A, an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO2. Then, an alloy film 13 made of Cu and Mn (auxiliary film containing a predetermined metal element α) is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12. The alloy film 13 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm. The Mn content in the alloy film 13 is set to be 0.05 to 20 at % (atomic percentage). The alloy film 13 works as a seed layer for forming a Cu main film by electrolytic plating described later.
Then, a heat treatment is performed on the structure shown in FIG. 1A, at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes. With this operation, Mn in the alloy film 13 is supplied with a force in directions to remove it from Cu, and thereby diffuses onto the surface of the interlevel insulating film 11 facing the alloy film 13. Mn thus supplied from the alloy film 13 reacts with O used as a component element of the interlevel insulating film 11. As a consequence, as shown in FIG. 1B, a barrier film 14 containing, as the main component, a very stable compound or oxide made of MnO is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11, and have a thickness of 5 nm or less, e.g., 2 nm. At this time, the portion of the alloy film 13 on the reverse side to the interlevel insulating film 11 is transformed into a Cu film 15 with a low Mn content.
Then, as shown in FIG. 1C, a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a. Thereafter, although not shown, the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by a planarization process, such as CMP (Chemical Mechanical Polishing), so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12.
Second Embodiment
As shown in FIG. 2A, an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO2. Then, an alloy film 13 made of Cu and Mn (auxiliary film containing a predetermined metal element α) is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12. The alloy film 13 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm. The Mn content in the alloy film 13 is set to be 0.05 to 20 at % (atomic percentage).
Then, as shown in FIG. 2B, a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a. Then, a heat treatment is performed on the structure shown in FIG. 2B, at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
With this operation, Mn in the alloy film 13 diffuses onto the surface of the interlevel insulating film 11 facing the alloy film 13. Mn thus supplied from the alloy film 13 reacts with O used as a component element of the interlevel insulating film 11. As a consequence, as shown in FIG. 2C, a barrier film 14 containing, as the main component, a very stable compound or oxide made of MnO is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11, and have a thickness of 5 nm or less, e.g., 2 nm. At this time, the portion of the alloy film 13 on the reverse side to the interlevel insulating film 11 is essentially integrated with the interconnection main layer formed of the Cu layer 16 a.
Thereafter, although not shown, the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12.
Third Embodiment
As shown in FIG. 3A, an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO2. Then, a Cu film 17 and a Mn film 18 are formed in this order on the interlevel insulating film 11 to cover the inner surface of the groove 12. The Cu film 17 and Mn film 18 compose an auxiliary film with a multi layered structure containing a predetermined metal element α. The Cu film 17 and Mn film 18 are formed by, e.g., sputtering to have a thickness of 5 to 100 nm and a thickness of 5 to 100 nm, respectively.
Then, a heat treatment is performed on the structure shown in FIG. 3A, at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes. With this operation, Mn in the Mn film 18 diffuses onto the surface of the interlevel insulating film 11 facing the Cu film 17. Mn thus supplied from the Mn film 18 reacts with O used as a component element of the interlevel insulating film 11. As a consequence, as shown in FIG. 3B, a barrier film 14 containing, as the main component, a very stable compound or oxide made of MnO is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11, and have a thickness of 5 nm or less, e.g., 2 nm. At this time, a Cu film 15 with a low Mn content is formed on the side of the barrier film 14 reverse to the interlevel insulating film 11.
Then, as shown in FIG. 3C, a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a. Thereafter, although not shown, the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12.
Fourth Embodiment
As shown in FIG. 4A, an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO2. Then, a Cu film 17 and a Mn film 18 are formed in this order on the interlevel insulating film 11 to cover the inner surface of the groove 12. The Cu film 17 and Mn film 18 compose an auxiliary film with a multi layered structure containing a predetermined metal element α. The Cu film 17 and Mn film 18 are formed by, e.g., sputtering to have a thickness of 5 to 100 nm and a thickness of 5 to 100 nm, respectively.
Then, as shown in FIG. 4B, a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a. Then, a heat treatment is performed on the structure shown in FIG. 4B, at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
With this operation, Mn in the Mn film 18 diffuses onto the surface of the interlevel insulating film 11 facing the Cu film 17. Mn thus supplied from the Mn film 18 reacts with O used as a component element of the interlevel insulating film 11. As a consequence, as shown in FIG. 4C, a barrier film 14 containing, as the main component, a very stable compound or oxide made of MnO is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11, and have a thickness of 5 nm or less, e.g., 2 nm.
Thereafter, although not shown, the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12.
Fifth Embodiment
As shown in FIG. 5A, an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO2. Then, a Mn film 18 and a Cu film 17 are formed in this order on the interlevel insulating film 11 to cover the inner surface of the groove 12. The Mn film 18 and Cu film 17 compose an auxiliary film with a multi layered structure containing a predetermined metal element α. The Mn film 18 and Cu film 17 are formed by, e.g., sputtering to have a thickness of 5 to 100 nm and a thickness of 5 to 100 nm, respectively.
Then, as shown in FIG. 5B, a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a. Then, a heat treatment is performed on the structure shown in FIG. 5B, at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
With this operation, Mn in the Mn film 18 diffuses onto the surface of the interlevel insulating film 11 facing the Mn film 18. Mn thus supplied from the Mn film 18 reacts with O used as a component element of the interlevel insulating film 11. As a consequence, as shown in FIG. 5C, a barrier film 14 containing, as the main component, a very stable compound or oxide made of MnO is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11, and have a thickness of 5 nm or less, e.g., 2 nm. At this time, the Cu film 17 is essentially integrated with the interconnection main layer formed of the Cu layer 16 a.
Thereafter, although not shown, the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12.
As a modification of the fifth embodiment, a heat treatment for diffusing Mn may be performed before forming the Cu main film 16, as in the first and third embodiments.
Sixth Embodiment
As shown in FIG. 6A, an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO2. Then, a Mn film (auxiliary film containing a predetermined metal element α) 18 is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12. The Mn film 18 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm.
Then, as shown in FIG. 6B, a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a. Then, a heat treatment is performed on the structure shown in FIG. 6B, at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
With this operation, Mn in the Mn film 18 diffuses onto the surface of the interlevel insulating film 11 facing the Mn film 18. Mn thus supplied from the Mn film 18 reacts with O used as a component element of the interlevel insulating film 11. As a consequence, as shown in FIG. 6C, a barrier film 14 containing, as the main component, a very stable compound or oxide made of MnO is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11, and have a thickness of 5 nm or less, e.g., 2 nm.
Thereafter, although not shown, the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12.
As a modification of the sixth embodiment, a heat treatment for diffusing Mn may be performed before forming the Cu main film 16, as in the first and third embodiments.
Seventh Embodiment
As shown in FIG. 7A, an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO2. Then, an alloy film 13 made of Cu and Mn (auxiliary film containing a predetermined metal element α) is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12. The alloy film 13 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm. The Mn content in the alloy film 13 is set to be 0.05 to 20 at % (atomic percentage).
Then, as shown in FIG. 7B, a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a. Then, a heat treatment is performed on the structure shown in FIG. 7B, at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes. At this time, the heat treatment is performed within an atmosphere containing oxygen, such as an inactive gas atmosphere of, e.g., Ar, containing O2 at a volume ratio of 1 ppm to 10%.
With this operation, Mn in the alloy film 13 is supplied with a force in directions to remove it from Cu, and thereby diffuses onto the surface of the interlevel insulating film 11 facing the alloy film 13, and also diffuses to the upper surface of the Cu main film 16. Mn thus supplied from the alloy film 13 reacts with O used as a component element of the interlevel insulating film 11, and with O present within the heat treatment atmosphere. As a consequence, as shown in FIG. 7C, a barrier film 14 containing MnO as the main component is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11, and have a thickness of 5 nm or less, e.g., 2 nm. Further, an insulating film (reaction product film) 19 containing MnO as the main component is also formed to cover the upper surface of the Cu main film 16.
Thereafter, although not shown, the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed along with the insulating film 19 by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12. According to the seventh embodiment, since Mn also diffuses to the upper surface of the Cu main film 16, Mn is scarcely left in the Cu layer 16 a, thereby preventing an increase in interconnection resistance.
As a modification of the seventh embodiment, the auxiliary film containing a predetermined metal element α may be a multi layered structure formed of a Cu film 17 and a Mn film 18, as in the fourth embodiment. Also in this modification, a heat treatment for diffusing Mn is performed within an atmosphere containing oxygen, so that the same effects can be obtained.
Eighth Embodiment
As shown in FIG. 8A, an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO2. Then, an alloy film 13 made of Cu and Mn (auxiliary film containing a predetermined metal element α) is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12. The alloy film 13 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm. The Mn content in the alloy film 13 is set to be 0.05 to 20 at % (atomic percentage).
Then, as shown in FIG. 8B, a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a. Then, an upper insulating film 20 containing oxygen, such as a SiO2 film, or SiC, SiCN, or SiN film containing oxygen, is formed on the upper surface of the Cu main film 16. Then, a heat treatment is performed on the structure shown in FIG. 8B, at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
With this operation, Mn in the alloy film 13 is supplied with a force in directions to remove it from Cu, and thereby diffuses onto the surface of the interlevel insulating film 11 facing the alloy film 13, and also diffuses to the upper surface of the Cu main film 16. Mn thus supplied from the alloy film 13 reacts with O used as a component element of the interlevel insulating film 11, and with O used as a component element of the upper insulating film 20. As a consequence, as shown in FIG. 8C, a barrier film 14 containing MnO as the main component is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11, and have a thickness of 5 nm or less, e.g., 2 nm. Further, an insulating film (reaction product film) 19 containing MnO as the main component is also formed to cover the upper surface of the Cu main film 16.
Thereafter, although not shown, the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed along with the insulating film 19 and upper insulating film 20 by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12.
As a modification of the eighth embodiment, the auxiliary film containing a predetermined metal element α may be a multi layered structure formed of a Cu film 17 and a Mn film 18, as in the fourth embodiment. Also in this modification, a heat treatment for diffusing Mn is performed after forming the upper insulating film 20 containing oxygen, so that the same effects can be obtained.
Ninth Embodiment
As shown in FIG. 9A, an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO2. Then, an alloy film 13 made of Cu and Mn (auxiliary film containing a predetermined metal element α) is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12. The alloy film 13 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm. The Mn content in the alloy film 13 is set to be 0.05 to 20 at % (atomic percentage).
Then, as shown in FIG. 9B, a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a. Then, the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12. Then, a heat treatment is performed on the structure shown in FIG. 9B, at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes. At this time, the heat treatment is performed within an atmosphere containing oxygen, such as an inactive gas atmosphere of, e.g., Ar, containing O2 at a volume ratio of 1 ppm to 10%.
With this operation, Mn in the alloy film 13 is supplied with a force in directions to remove it from Cu, and thereby diffuses onto the surface of the interlevel insulating film 11 facing the alloy film 13, and also diffuses to the upper surface of the Cu layer 16 a. Mn thus supplied from the alloy film 13 reacts with O used as a component element of the interlevel insulating film 11, and with O present within the heat treatment atmosphere. As a consequence, as shown in FIG. 9C, a barrier film 14 containing MnO as the main component is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11, and have a thickness of 5 nm or less, e.g., 2 nm. Further, an upper barrier film 14 a containing MnO as the main component is also formed to cover the upper surface of the Cu layer 16 a. The upper barrier film can be used as a film for preventing Cu from diffusing from the Cu layer 16 a into an interlevel insulating film further formed thereon.
As a modification of the ninth embodiment, the auxiliary film containing a predetermined metal element α may be a multi layered structure formed of a Cu film 17 and a Mn film 18, as in the fourth embodiment. Also in this modification, a heat treatment for diffusing Mn is performed within an atmosphere containing oxygen after CMP, so that the same effects can be obtained.
Tenth Embodiment
As shown in FIG. 10A, an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO2. Then, an alloy film 13 made of Cu and Mn (auxiliary film containing a predetermined metal element α) is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12. The alloy film 13 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm. The Mn content in the alloy film 13 is set to be 0.05 to 20 at % (atomic percentage).
Then, as shown in FIG. 10B, a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a. Then, the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12. Then, an upper insulating film 20 containing oxygen, such as a SiO2 film, or SiC, SiCN, or SiN film containing oxygen, is formed on the upper surface of the Cu layer 16 a. Then, a heat treatment is performed on the structure shown in FIG. 10B, at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
With this operation, Mn in the alloy film 13 is supplied with a force in directions to remove it from Cu, and thereby diffuses onto the surface of the interlevel insulating film 11 facing the alloy film 13, and also diffuses to the upper surface of the Cu layer 16 a. Mn thus supplied from the alloy film 13 reacts with O used as a component element of the interlevel insulating film 11, and with O used as a component element of the upper insulating film 20. As a consequence, as shown in FIG. 10C, a barrier film 14 containing MnO as the main component is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11, and have a thickness of 5 nm or less, e.g., 2 nm. Further, an upper barrier film 14 a containing MnO as the main component is also formed to cover the upper surface of the Cu layer 16 a.
As a modification of the tenth embodiment, the auxiliary film containing a predetermined metal element α may be a multi layered structure formed of a Cu film 17 and a Mn film 18, as in the fourth embodiment. Also in this modification, a heat treatment for diffusing Mn is performed after performing CMP and then forming the upper insulating film 20 containing oxygen, so that the same effects can be obtained.
Eleventh Embodiment
As shown in FIG. 11A, an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO2. Then, a Cu film 17 is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12. The Cu film 17 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm. The Cu film 17 works as a seed layer for forming a Cu main film by electrolytic plating described later.
Then, as shown in FIG. 11B, a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a. Then, a Mn film (auxiliary film containing a predetermined metal element α) 18 is formed on the Cu main film 16. The Mn film 18 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm. Then, a heat treatment is performed on the structure shown in FIG. 11B, at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
With this operation, Mn in the Mn film 18 diffuses onto the surface of the interlevel insulating film 11 facing the Cu film 17. Mn thus supplied from the Mn film 18 reacts with O used as a component element of the interlevel insulating film 11. As a consequence, as shown in FIG. 1C, a barrier film 14 containing, as the main component, a very stable compound or oxide made of MnO is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11, and have a thickness of 5 nm or less, e.g., 2 nm. At this time, the Cu film 17 is essentially integrated with the interconnection main layer formed of the Cu layer 16 a.
Thereafter, although not shown, the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12.
Twelfth Embodiment
As shown in FIG. 12A, an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO2. Then, a Cu film 17 is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12. The Cu film 17 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm.
Then, as shown in FIG. 12B, a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a. Then, a Mn film (auxiliary film containing a predetermined metal element α) 18 is formed on the Cu main film 16. The Mn film 18 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm. Then, a heat treatment is performed on the structure shown in FIG. 12B, at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes. At this time, the heat treatment is performed within an atmosphere containing oxygen, such as an inactive gas atmosphere of, e.g., Ar, containing O2 at a volume ratio of 1 ppm to 10%.
With this operation, Mn in the Mn film 18 diffuses onto the surface of the interlevel insulating film 11 facing the Cu film 17, and also stays at the upper surface of the Cu main film 16 due to an influence of oxygen contained in the heat treatment atmosphere. Mn thus supplied from the Mn film 18 reacts with O used as a component element of the interlevel insulating film 11, and with O present within the heat treatment atmosphere. As a consequence, as shown in FIG. 12C, a barrier film 14 containing MnO as the main component is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11, and have a thickness of 5 nm or less, e.g., 2 nm. Further, an insulating film (reaction product film) 19 containing MnO as the main component is also formed to cover the upper surface of the Cu main film 16.
Thereafter, although not shown, the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed along with the insulating film 19 by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12.
Thirteenth Embodiment
As shown in FIG. 13A, an interconnection groove (opening) 12 is formed in an interlevel insulating film 11 made of SiO2. Then, a Cu film 17 is formed on the interlevel insulating film 11 to cover the inner surface of the groove 12. The Cu film 17 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm.
Then, as shown in FIG. 13B, a Cu main film 16 used as the material of an interconnection main layer is formed by electrolytic plating to fill the interconnection groove 12 with a Cu layer 16 a. Then, a Mn film (auxiliary film containing a predetermined metal element α) 18 is formed on the Cu main film 16. The Mn film 18 is formed by, e.g., sputtering to have a thickness of 5 to 100 nm. Then, an upper insulating film 20 containing oxygen, such as a SiO2 film, or SiC, SiCN, or SiN film containing oxygen, is formed on the Mn film 18. Then, a heat treatment is performed on the structure shown in FIG. 13B, at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
With this operation, Mn in the Mn film 18 diffuses onto the surface of the interlevel insulating film 11 facing the alloy film 13, and also stays at the upper surface of the Cu main film 16 due to an influence of oxygen contained in the upper insulating film 20 as a component element. Mn thus supplied from the Mn film 18 reacts with O used as a component element of the interlevel insulating film 11, and with O used as a component element of the upper insulating film 20. As a consequence, as shown in FIG. 13C, a barrier film 14 containing MnO as the main component is formed by means of self alignment to cover the inner surface of the interlevel insulating film 11, and have a thickness of 5 nm or less, e.g., 2 nm. Further, an insulating film (reaction product film) 19 containing MnO as the main component is also formed to cover the upper surface of the Cu main film 16.
Thereafter, although not shown, the portion of the Cu main film 16 outside the interconnection groove 12 is polished and removed along with the insulating film 19 and upper insulating film 20 by, e.g., CMP, so that the interconnection main layer formed of the Cu layer 16 a and having a low resistance is left in the interconnection groove 12.
(Matters Common to the First to Thirteenth Embodiments)
FIG. 14 is a view showing characteristics of various Cu alloys, in terms of change in resistivity relative to heat treatment temperature. In FIG. 14, the horizontal axis denotes heat treatment temperature T(° C.), and the vertical axis denotes alloy resistivity R (μΩcm). Where an alloy is formed of Cu with Ni, Mg, or Al, the resistivity greatly increases when the heat treatment temperature exceeds 350° C. By contrast, where an alloy is formed of Cu with Mn, the resistivity decreases to be equal to that of pure copper as the heat treatment temperature is higher. This means that Mn used as the alloy element does not stay as solid solution in the Cu film, but moves to the interface, thereby reducing the resistivity to be equal to that of pure copper. Accordingly, Mn used as the alloy element can realize an interconnection with a lower resistance, as compared to conventional interconnections.
FIG. 15 is a view showing a TEM micrographic image of a cross section of a semiconductor device manufactured by the first embodiment. As shown in FIG. 15, a barrier film 14 made of MnO (it can be expressed more properly by MnxSiyOz (x:y:z=1:1:3 to 1:3:5)) and having a thickness of about 3 nm is uniformly formed between a Cu layer 16 a and an interlevel insulating film 11. In other words, a stable compound is formed at the interface between the Cu layer 16 a and interlevel insulating film 11.
As described above, according to the first embodiment, an alloy film of Cu with Mn is employed and formed as an auxiliary film containing Mn or a predetermined metal element α, and is then subjected to a heat treatment. With this operation, a MnO barrier film is formed by means of self alignment at the interface between the alloy film and the interlevel insulating film or SiO2 film. The resistivity of the portion where the alloy film was formed becomes as low as pure copper, after the heat treatment. As a consequence, a Cu interconnection is formed by a barrier self formation process without increasing the electric resistance of the interconnection, thereby improving the reliability of the interconnection structure and reducing the interconnection resistance. The same effects can be also attained in any one of the second to thirteenth embodiments described above.
The methods described above according to the first to thirteenth embodiments are preferably applicable to a damascene interconnection structure, as shown in the following embodiments.
Fourteenth Embodiment
FIGS. 16A to 16F are sectional views showing sequential steps of a semiconductor device manufacturing method according to a fourteenth embodiment of the present invention. In this embodiment, the first embodiment is applied to a dual damascene interconnection structure.
As shown in FIG. 16A, an interlevel insulating film 31 formed of, e.g., a SiO2 film is disposed with an interconnection groove formed in the surface thereof, on a semiconductor substrate Sub. The interconnection groove is filled with a Cu layer (lower interconnection layer (i.e., conductive layer)) 33 with a barrier film 32 interposed therebetween. The barrier film 32 and Cu layer 33 may be prepared by a method according to any one of the first to thirteenth embodiments.
On the structure described above, as shown in FIG. 16A, a diffusion prevention film (lower insulating film) 34, such as SiN or SiCN, is formed. Then, as shown in FIG. 16B, an interlevel insulating film 41 made of SiO2 is deposited to have a thickness of 150 to 600 nm. Then, an opening 42 is formed in the interlevel insulating film 41 to include an interconnection hole 42 a for connection to the Cu layer 33 and an interconnection groove 42 b.
Then, as shown in FIG. 16C, an alloy film 43 made of Cu and Mn (auxiliary film containing a predetermined metal element α) is formed by, e.g., CVD to cover the inner surface of the opening 42 and have a thickness of 5 to 100 nm. Then, as shown in FIG. 16D, a heat treatment is performed at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
With this operation, a barrier film 44 containing MnO as the main component is formed to cover the inner surface of the opening 42 of the interlevel insulating film 41. At this time, at the bottom of the interconnection hole 42 a, since no interlevel insulating film 41 is present, no barrier film 44 is formed, but only a Cu film 45 is formed. Accordingly, a Cu upper interconnection layer formed later will come into essentially direct contact with the Cu layer (lower interconnection layer) 33 with no barrier film 44 interposed therebetween.
Then, as shown in FIG. 16E, a Cu main film 46 having a thickness of 0.8 to 1 μm is deposited all over by electrolytic plating to fill the opening 42 with the Cu main film (upper interconnection layer) 46. Then, as shown in FIG. 16F, the unnecessary portion of the Cu main film 46 is removed by CMP to planarize the structure surface. Then, a diffusion prevention film 49, such as a SiC, SiCN, or SiN film, is formed all over the structure surface.
The alloy film 43 may be formed by any one of PVD, CVD, and electroless plating methods. In the case of the CVD method, a source gas containing Mn is employed. In the case of the electroless plating method, a plating solution containing Mn is employed. The Cu Mn alloy film 43 preferably contains 0.05 to 20% Mn by atomic percentage. The heat treatment for diffusing Mn to the surface of the interlevel insulating film 41 is preferably performed at a temperature of 50 to 400° C. for 60 minutes or less.
According to this semiconductor device having a dual damascene structure thus manufactured, the barrier film 44 containing MnO as the main component is formed by means of self alignment at the interface between the Cu main film 46 used as an interconnection main layer and the SiO2 interlevel insulating film 41. The Cu main film 46 used as an upper interconnection layer is in essentially direct contact with the Cu lower interconnection layer 33 with no barrier film interposed therebetween, and the contact resistance between the interconnection layers is thereby reduced. As a consequence, a Cu interconnection is formed by barrier self formation process without increasing the electric resistance of the interconnection, thereby improving the reliability of the interconnection structure and reducing the interconnection resistance.
FIG. 17 is a sectional view showing a semiconductor device according to a modification of the fourteenth embodiment. As shown in FIG. 17, where a positional deviation is present between a lower interconnection layer 33 and an upper interconnection layer 46, an interconnection hole 42 a may partly deviate from the lower interconnection layer 33. In this case, a barrier film 44 is formed on an interlevel insulating film 31 even to the bottom of the interconnection hole 42 a, and thus a part of the barrier film 44 is present at the bottom of the opening 42. However, no barrier film 44 is formed between the upper and lower interconnection layers 46 and 33. Accordingly, unless the positional deviation is excessively large, the upper and lower interconnection layers 46 and 33 have sufficient contact therebetween.
Although the first embodiment is utilized in this embodiment, the same effects can be attained where any one of the second to thirteenth embodiments is utilized.
Fifteenth Embodiment
FIG. 18 is a sectional view showing a semiconductor device according to a fifteenth embodiment of the present invention. In this embodiment, the first embodiment is applied to a single damascene interconnection structure. This device may be manufactured by a method almost the same as that of the fourteenth embodiment, except for the following points.
Specifically, on the structure shown in FIG. 16A, an interlevel insulating film 51 made of SiO2 and having a thickness of 150 to 300 nm is deposited, and an interconnection hole 52 for connection to a lower interconnection layer 33 is formed therein. Then, a Cu Mn alloy film is formed by, e.g., CVD to cover the inner surface of the interconnection hole 52 and have a thickness of 5 to 100 nm. Then, a heat treatment is performed to form a MnO barrier film 54 on the inner surface of the hole of the interlevel insulating film 51. Then, a Cu film 56 is formed to fill the interconnection hole 52, and the unnecessary portion of the Cu film 56 is removed by CMP.
Then, an interlevel insulating film 61, an interconnection groove 62, a MnO barrier film 64, and a Cu film 66 are formed by the same processes used for the parts 51 to 56. Then, the unnecessary portion of the Cu film 66 is removed by CMP, and a diffusion prevention film 49 is formed.
Also in this arrangement, the MnO barrier films 54 and 64 are formed between the Cu films 56 and 66 filling the interconnection hole 52 and interconnection groove 62, and the interlevel insulating films 51 and 61. The Cu film 56 used as a connection plug is in direct contact with the Cu lower interconnection layer 33, and the Cu film 66 used as an upper interconnection layer is in direct contact with the Cu film 56. As a consequence, the fifteenth embodiment provides the same effects as the fourteenth embodiment.
Sixteenth Embodiment
FIGS. 19A to 19C are sectional views showing sequential steps of a semiconductor device manufacturing method according to a sixteenth embodiment of the present invention. In this embodiment, the tenth embodiment is applied to a dual damascene interconnection structure.
On the structure shown in FIG. 16C with a Cu Mn alloy layer 43 formed thereon, a Cu main film 46 is formed to fill the opening 42, as shown in FIG. 19A. Then, the unnecessary portion of the Cu main film 46 is removed by CMP to planarize the surface. Then, an upper insulating film 79 containing oxygen, such as a SiO2 film, is formed on the upper surface of the Cu main film 46. Then, a heat treatment is performed on the structure shown in FIG. 19A, at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes.
With this operation, a barrier film 44 containing MnO as the main component is formed to cover the inner surface of the opening 42 of the interlevel insulating film 41. At this time, at the bottom of the interconnection hole 42 a, since no interlevel insulating film 41 is present, no barrier film 44 is formed. Accordingly, the upper and lower interconnection layers 46 and 33 are in essentially direct contact with each other with no barrier film 44 interposed therebetween. Further, since the oxide film 79 is present on the upper surface of the Cu main film 46, Mn diffuses there, thereby forming an upper barrier film (reaction product film) 47 containing MnO as the main component.
Then, as shown in FIG. 19C, the upper insulating film 79 is removed. As a consequence, only the upper barrier film 47 functioning as a barrier film is left on the Cu main film 46 (no barrier film 47 is present above the interlevel insulating film 41).
In addition to the same effects as the fourteenth embodiment, this embodiment can provide the following effects because of the upper barrier film 47 present only on the Cu main film 46. Specifically, in general, a Cu embedded interconnection structure requires a diffusion prevention film with a high dielectric constant, such as a SiC, SiCN, or SiN film, to be disposed on the Cu main film 46. Where such a diffusion prevention film is disposed all over the structure surface, the capacitance between adjacent interconnections becomes higher due to the presence of the diffusion prevention film. By contrast, in this embodiment, the barrier film 47 disposed on the Cu main film 46 functions as a protection film, and thus requires no additional diffusion prevention film to be formed. Accordingly, there is no high dielectric constant film, such as a nitride film, present between adjacent interconnections, thereby reducing the capacitance between the adjacent interconnections.
Seventeenth Embodiment
FIGS. 20A to 20E are sectional views showing sequential steps of a semiconductor device manufacturing method according to a seventeenth embodiment of the present invention. In this embodiment, the seventh embodiment is applied to a dual damascene interconnection structure.
As shown in FIG. 20A, an interlevel insulating film 81 formed of, e.g., a SiO2 film is disposed with an interconnection groove formed in the surface thereof, on a semiconductor substrate Sub. The interconnection groove is filled with a Cu layer (lower interconnection layer (i.e., conductive layer)) 83 with a barrier film 82 interposed therebetween. The barrier film 82 and Cu layer 83 may be prepared by a method according to any one of the first to thirteenth embodiments.
On the structure described above, as shown in FIG. 20A, a diffusion prevention film (lower insulating film) 84 is formed. The diffusion prevention film 84 is made of, e.g., SiN or SiCN containing oxygen at a concentration of 33% or less by atomic percentage, and having an atomic density higher than the interlevel insulating film 81. Then, as shown in FIG. 20B, an interlevel insulating film 91 made of SiO2 is deposited to have a thickness of 150 to 600 nm. Then, an opening 92 is formed in the interlevel insulating film 91 to include an interconnection hole 92 a for connection to the Cu layer (lower interconnection layer) 83 and an interconnection groove 92 b. At this time, the interconnection hole 92 a is formed to pass through the diffusion prevention film 84 and reach the lower interconnection layer 83.
Then, as shown in FIG. 20C, an alloy film 93 made of Cu and Mn (auxiliary film containing a predetermined metal element α) is formed by, e.g., CVD to cover the inner surface of the opening 92 and have a thickness of 5 to 100 nm. Then, a Cu main film 96 having a thickness of 0.8 to 1 μm is deposited all over by electrolytic plating to fill the opening 92 with the Cu main film (upper interconnection layer) 96. Then, a heat treatment is performed on the structure shown in FIG. 20C, at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes. At this time, the heat treatment is performed within an atmosphere containing oxygen, such as an inactive gas atmosphere of, e.g., Ar, containing O2 at a volume ratio of 1 ppm to 10%.
With this operation, as shown in FIG. 20D, a barrier film 94 containing MnO as the main component is formed to cover the inner surface of the opening 92 of the interlevel insulating film 91. Further, since the upper surface of the Cu main film 96 is exposed to the atmosphere containing oxygen, Mn diffuses there, thereby forming an insulating film (reaction product film) 97 containing MnO as the main component.
Then, as shown in FIG. 20E, the unnecessary portion of the Cu main film 96 is removed along with the insulating film 97 by CMP to planarize the structure surface. Then, a diffusion prevention film 99, such as a SiN or SiCN film, is formed all over the structure surface.
According to this embodiment, the diffusion prevention film 84 interposed between the lower interconnection layer 83 and interlevel insulating film 91 contains oxygen. As a consequence, the barrier film 94 containing MnO as the main component is reliably formed by means of self alignment also on the inner surface of the portion 92 s of the interconnection hole 92 a passing through the diffusion prevention film 84. This can prevent defects from being generated in the barrier film 94 at this portion 92 s, which would allow Cu to diffuse through from the interconnection layer.
FIG. 21 is a graph showing the oxygen concentration distribution in the diffusion prevention film 84 according to a modification of the seventeenth embodiment. In FIG. 21, the horizontal axis denotes the position Th (nm) of the diffusion prevention film 84 in the film thickness direction, relative to the surface of the lower interconnection layer 83 used as the reference point, and the vertical axis denotes the oxygen concentration Con O (atomic %) in the diffusion prevention film 84.
Where the oxygen concentration in the diffusion prevention film 84 is high near the lower interconnection layer 83, Cu in the lower interconnection layer 83 may be oxidized, thereby deteriorating device properties. For this reason, in this modification, the oxygen concentration in the diffusion prevention film 84 is set lower on the lower interconnection layer 83 side than on the interlevel insulating film 91 side.
As a method of forming such a diffusion prevention film 84, a method of depositing the film 84 by CVD may be arranged such that the oxygen concentration in the process atmosphere is set lower at first, and is then gradually increased. Alternatively, the diffusion prevention film 84 may have a multi layered structure formed of a lower layer of several nm and an upper layer both deposited by CVD, in which only the lower layer has a lower oxygen concentration, while the upper layer has a sufficiently high oxygen concentration.
Eighteenth Embodiment
FIGS. 22A to 22E are sectional views showing sequential steps of a semiconductor device manufacturing method according to an eighteenth embodiment of the present invention. This embodiment is a modification of the seventeenth embodiment.
As shown in FIG. 22A, an interlevel insulating film 81 is disposed with an interconnection groove formed in the surface thereof, on a semiconductor substrate Sub. The interconnection groove is filled with a Cu layer (lower interconnection layer) 83 with a barrier film 82 interposed therebetween. The barrier film 82 and Cu layer 83 may be prepared by a method according to any one of the first to thirteenth embodiments.
On the structure described above, as shown in FIG. 22A, a refractory metal layer 104 is formed on the barrier film 82 and Cu layer 83. The refractory metal layer 104 is made of, e.g., CoW, CoWB, CoWP, or CuSi to prevent the lower interconnection layer 83 from being oxidized or causing Cu diffusion. Then, as shown in FIG. 22B, an interlevel insulating film 111 made of SiO2 is deposited to have a thickness of 150 to 600 nm. Then, an opening 112 is formed in the interlevel insulating film 111 to include an interconnection hole 112 a for connection to the Cu layer 83 and an interconnection groove 112 b. At this time, the interconnection hole 112 a is formed to terminate on the upper surface of the refractory metal layer 104.
Then, as shown in FIG. 22C, an alloy film 113 made of Cu and Mn (auxiliary film containing a predetermined metal element α) is formed by, e.g., CVD to cover the inner surface of the opening 112 and have a thickness of 5 to 100 nm. Then, a Cu main film 116 having a thickness of 0.8 to 1 μm is deposited all over by electrolytic plating to fill the opening 112 with the Cu main film (upper interconnection layer) 116. Then, a heat treatment is performed on the structure shown in FIG. 22C, at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes. At this time, the heat treatment is performed within an atmosphere containing oxygen, such as an inactive gas atmosphere of, e.g., Ar, containing O2 at a volume ratio of 1 ppm to 10%.
With this operation, as shown in FIG. 22D, a barrier film 114 containing MnO as the main component is formed to cover the inner surface of the opening 112 of the interlevel insulating film 111. Further, since the upper surface of the Cu main film 116 is exposed to the atmosphere containing oxygen, Mn diffuses there, thereby forming an insulating film (reaction product film) 117 containing MnO as the main component.
Then, as shown in FIG. 22E, the unnecessary portion of the Cu main film 116 is removed along with the insulating film 117 by CMP to planarize the structure surface. Then, a diffusion prevention film 119, such as a SiN or SiCN film, is formed all over the structure surface.
According to this embodiment, since the upper surface of the lower interconnection layer 83 is covered with the refractory metal layer 104, the lower interconnection layer 83 is prevented from being oxidized or causing Cu diffusion.
FIG. 23 is a sectional view showing a semiconductor device according to a modification of the eighteenth embodiment. In this modification, an interconnection hole 112 a formed in the interlevel insulating film 111 further passes through the refractory metal layer 104 and reaches the lower interconnection layer 83. In this case, the upper and lower interconnection layers 116 and 83 are in direct contact with each other, thereby reducing the interconnection resistance.
Nineteenth Embodiment
FIGS. 24A to 24F are sectional views showing sequential steps of a semiconductor device manufacturing method according to a nineteenth embodiment of the present invention. This embodiment is another modification of the seventeenth embodiment.
As shown in FIG. 24A, an interlevel insulating film 121 is disposed with an interconnection groove formed in the surface thereof, on a semiconductor substrate Sub. The interlevel insulating film 121 is formed of a low dielectric constant film, such as a porous SiO2, SiC, SiOC, SiOCH, or SiCOF film. The interconnection groove is filled with a Cu layer (lower interconnection layer (i.e., conductive layer)) 123 with a barrier film 122 interposed therebetween. The barrier film 122 and Cu layer 123 may be prepared by a method according to any one of the first to thirteenth embodiments.
On the structure described above, as shown in FIG. 24A, a diffusion prevention film (lower insulating film) 124, an interlevel insulating film 125, and an etching stop film 126 are formed in this order. The diffusion prevention film 124 is made of, e.g., SiN or SiCN having an atomic density higher than the interlevel insulating film 121, but containing essentially no oxygen unlike the diffusion prevention film 84 describe above. The interlevel insulating film 125 consists of a porous low dielectric constant film, essentially the same as that used for the interlevel insulating film 121. The etching stop film 126 is made of an insulating material, such as SiN, SiCN, or polymer material, e.g., PAE (polyallylene), which contains oxygen at a concentration of 33% or less by atomic percentage, and has an atomic density higher than the interlevel insulating films 121 and 125.
Then, as shown in FIG. 24B, an interlevel insulating film 127 consisting of a porous low dielectric constant film, the same as that used for the interlevel insulating film 121, is formed on the etching stop film 126. Then, an opening 132 is formed in the interlevel insulating film 127 and diffusion prevention film 124 to include an interconnection hole 132 a for connection to the Cu layer (lower interconnection layer) 123 and an interconnection groove 132 b. At this time, the interconnection groove 132 b is formed to terminate on the etching stop film 126, and the interconnection hole 132 a is formed to extend therefrom through the diffusion prevention film 124 onto the lower interconnection layer 123. Then, a coating film 128, which is made of an insulating material containing oxygen and having a higher atomic density, i.e., the same material as the etching stop film 126, is formed to cover the inner surface of the opening 132.
Then, as shown in FIG. 24C, anisotropic etching is performed vertically from above by RIE, to remove the portion of the coating film 128 at the bottom of the interconnection hole 132 a, so that the lower interconnection layer 123 is exposed. At this time, the portion of the coating film 128 on the etching stop film 126 is also removed, and the etching stop film 126 is thereby exposed.
Then, as shown in FIG. 24D, an alloy film 133 made of Cu and Mn (auxiliary film containing a predetermined metal element α) is formed by, e.g., CVD to cover the inner surface of the opening 132 (surfaces of the etching stop film 126 and coating film 128) and have a thickness of 5 to 100 nm. Then, a Cu main film 136 having a thickness of 0.8 to 1 μm is deposited all over by electrolytic plating to fill the opening 132 with the Cu main film (upper interconnection layer) 136. Then, a heat treatment is performed on the structure shown in FIG. 24D, at a temperature of 200 to 400° C. for 5 to 30 minutes, e.g., at 300° C. for 5 minutes. At this time, the heat treatment is performed within an atmosphere containing oxygen, such as an inactive gas atmosphere of, e.g., Ar, containing O2 at a volume ratio of 1 ppm to 10%.
With this operation, as shown in FIG. 24E, a barrier film 134 containing MnO as the main component is formed to cover the inner surface of the opening 132 of the interlevel insulating films 125 and 127. Further, since the upper surface of the Cu main film 136 is exposed to the atmosphere containing oxygen, Mn diffuses there, thereby forming an insulating film (reaction product film) 137 containing MnO as the main component.
Then, as shown in FIG. 24F, the unnecessary portion of the Cu main film 136 is removed along with the insulating film 137 by CMP to planarize the structure surface. Then, a diffusion prevention film 139, such as a SiN or SiCN film, is formed all over the structure surface.
According to this embodiment, the barrier film 134 containing MnO as the main component is formed while using oxygen present within the etching stop film 126 and coating film 128, which cover the interlevel insulating films 125 and 127. This makes it possible to arbitrarily choose the materials of the interlevel insulating films 125 and 127. For example, as in this embodiment, porous low dielectric constant films are used as the interlevel insulating films 125 and 127 to improve the operation speed of the device.
(Matters Common to the First to Nineteenth Embodiments)
The embodiment described above is exemplified by a case where Cu is used as the material of the interconnection main layer. The interconnection main layer, however, may be made of another material containing Cu as the main component (i.e., by 50% or more), such as a Cu alloy commonly used as an interconnection material. Also in such a case, the same effects as described above can be attained.
The metal element α is not limited to Mn, and it may comprise at least one element selected from the group consisting of Mn, Nb, Zr, Cr, V, Y, Tc, and Re. These metal elements have the following advantages, as compared to Ti and Ta, which are used for conventional barrier films, and Al, Mg, and Sn, which have been proposed by conventional barrier less process techniques. Specifically, the metal elements listed above for the metal element α can easily form an oxide and the oxide is high in affinity with interlevel insulating films. Accordingly, they can provide a stable oxide layer with uniform quality and very small thickness between an interconnection main layer and an interlevel insulating film. Further, since these elements tend to precipitate or form a compound, rather than staying as solid solution in Cu, they do not increase the interconnection resistance.
The material of interlevel insulating films is not limited to SiO2, and various insulating films may be used. Where an interlevel insulating film contains a SiO bond group as the main component, such as SiO2, it forms αxOy or αxSiyOz by reaction with the metal element α. Where an interlevel insulating film contains an organic component, such as CC, it forms a compound containing this component element by reaction with the metal element α. In this latter case, the compound can function as a layer like MnO for preventing Cu diffusion, and provide the same effects as described above.
A method of filling or embedding the Cu film is not limited to a method utilizing electrolytic plating, and it may be a method utilizing CVD, PVD, electroless plating, or film formation using critical liquid. The same effects as described above can be attained by any method, as long as it can embed Cu within a groove and/or a hole formed in an insulating film.
The embodiments described above may be applied to any one of the interconnections from the lowermost level to the uppermost level in a multi layered interconnection structure disposed on a semiconductor substrate. In this respect, the fourteenth to nineteenth embodiments are exemplified by application to the second level interconnection, but may also be applied to the first level interconnection in the same way.
As an example, FIG. 25 is a sectional view showing a semiconductor device according to a modification of the fourteenth embodiment. Specifically, as shown in FIG. 25, aiming at an impurity diffusion layer (i.e., conductive layer) 40 formed in the surface of a semiconductor substrate Sub, a first level interconnection structure is formed by a method according to the fourteenth embodiment. The first level interconnection structure has a dual damascene interconnection structure, which includes an interlevel insulating film 41 1, a Cu layer 46 1, a MnO barrier film 44 1, and a diffusion prevention film 49 1. Further, aiming at the first level Cu layer 46 1, a second level interconnection structure is formed by a method according to the fourteenth embodiment. The second level interconnection structure has a dual damascene interconnection structure, which includes an interlevel insulating film 41 2, a Cu layer 46 2, a MnO barrier film 44 2, and a diffusion prevention film 49 2.
A multi layered interconnection structure, as shown in FIG. 25, may be manufactured in the same manner, using any of the other embodiments. If necessary, different embodiments selected from the first to thirteenth embodiments may be respectively applied to different level interconnection structures.
The fourteenth to nineteenth embodiments are exemplified by a case where a dual damascene or single damascene interconnection structure is used. The present invention, however, may be applied to various embedded interconnection structures other than damascene interconnection structures.
Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.

Claims (6)

1. A method of manufacturing a semiconductor device, comprising:
forming an opening in an interlevel insulating film disposed on a semiconductor substrate, the interlevel insulating film containing silicon atoms;
forming an auxiliary film containing a predetermined metal element, to cover an inner surface of the opening;
forming a main film to fill the opening after forming the auxiliary film, the main film containing, as a main component, Cu used as a material of an interconnection main layer; and
performing a heat treatment before or after forming the main film, thereby diffusing the predetermined metal element of the auxiliary film onto a surface of the interlevel insulating film facing the auxiliary film, so as to form a barrier film on the interlevel insulating film within the opening, the barrier film containing, as a main component, a compound of the predetermined metal element with the silicon atoms of the interlevel insulating film.
2. The method according to claim 1, further comprising forming an upper insulating film to cover an upper surface of the main film after forming the main film, wherein the heat treatment is thereafter performed, thereby diffusing the predetermined metal element of the auxiliary film also to the upper surface of the main film, so as to form a reaction product film on the upper surface, the reaction product film containing, as a main component, a compound of the predetermined metal element with a component element of the upper insulating film.
3. The method according to claim 1, wherein the heat treatment is performed within an atmosphere containing oxygen after forming the main film, thereby diffusing the predetermined metal element of the auxiliary film also to the upper surface of the main film, so as to form a reaction product film on the upper surface, the reaction product film containing, as a main component, an oxide of the predetermined metal element.
4. The method according to claim 1, wherein the predetermined metal element comprises at least one element selected from the group consisting of Mn, Nb, Zr, Cr, V, Y, Tc, and Re.
5. The method according to claim 1, further comprising forming a refractory metal layer and the interlevel insulating film in this order on a lower interconnection layer disposed on the semiconductor substrate, wherein the opening is formed to pass through the refractory metal layer.
6. The method according to claim 1, wherein the interlevel insulating film is a porous low dielectric constant film, and the method further comprises forming a coating film having a higher atomic density than the interlevel insulating film, to cover an inner surface of the opening, before forming the auxiliary film and the main film.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8836124B2 (en) 2012-03-08 2014-09-16 International Business Machines Corporation Fuse and integrated conductor
US9978878B2 (en) 2010-04-23 2018-05-22 Semiconductor Energy Laboratory Co., Ltd. Manufacturing method of semiconductor device
US10056494B2 (en) 2009-11-13 2018-08-21 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device and manufacturing method thereof
US10158005B2 (en) 2008-11-07 2018-12-18 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device
US11430817B2 (en) 2013-11-29 2022-08-30 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device

Families Citing this family (136)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4478038B2 (en) 2004-02-27 2010-06-09 株式会社半導体理工学研究センター Semiconductor device and manufacturing method thereof
JP4764606B2 (en) * 2004-03-04 2011-09-07 ルネサスエレクトロニクス株式会社 Semiconductor device and manufacturing method thereof
JP4851740B2 (en) * 2005-06-30 2012-01-11 株式会社東芝 Semiconductor device and manufacturing method thereof
JP4679270B2 (en) 2005-06-30 2011-04-27 株式会社東芝 Semiconductor device and manufacturing method thereof
JP2007012996A (en) * 2005-07-01 2007-01-18 Toshiba Corp Semiconductor device
JP4197694B2 (en) * 2005-08-10 2008-12-17 株式会社東芝 Semiconductor device and manufacturing method thereof
JP4236201B2 (en) * 2005-08-30 2009-03-11 富士通マイクロエレクトロニクス株式会社 Manufacturing method of semiconductor device
JP4523535B2 (en) * 2005-08-30 2010-08-11 富士通株式会社 Manufacturing method of semiconductor device
JP4282646B2 (en) 2005-09-09 2009-06-24 株式会社東芝 Manufacturing method of semiconductor device
JP2007109736A (en) * 2005-10-11 2007-04-26 Nec Electronics Corp Semiconductor device and method of manufacturing same
JP4946008B2 (en) * 2005-11-15 2012-06-06 ソニー株式会社 Semiconductor device and manufacturing method of semiconductor device
JP4529880B2 (en) 2005-11-21 2010-08-25 ソニー株式会社 Semiconductor device and manufacturing method of semiconductor device
JP2007149813A (en) * 2005-11-25 2007-06-14 Sony Corp Manufacturing method of semiconductor device
KR100702797B1 (en) * 2005-12-09 2007-04-03 동부일렉트로닉스 주식회사 Method of fabricating the copper interconnection layer in semiconductor device
JP2007173511A (en) * 2005-12-22 2007-07-05 Sony Corp Method for fabricating a semiconductor device
KR100720529B1 (en) * 2005-12-29 2007-05-22 동부일렉트로닉스 주식회사 Metal line of semiconductor device and method for forming the same
US7863183B2 (en) * 2006-01-18 2011-01-04 International Business Machines Corporation Method for fabricating last level copper-to-C4 connection with interfacial cap structure
JP5076482B2 (en) * 2006-01-20 2012-11-21 富士通セミコンダクター株式会社 Manufacturing method of semiconductor device
JP2007220738A (en) * 2006-02-14 2007-08-30 Sony Corp Method of manufacturing semiconductor device
US8372745B2 (en) 2006-02-28 2013-02-12 Advanced Interconnect Materials, Llc Semiconductor device, its manufacturing method, and sputtering target material for use in the method
WO2007100125A1 (en) 2006-02-28 2007-09-07 Advanced Interconnect Materials, Llc Semiconductor device, its manufacturing method, and sputtering target material for use in the method
EP1845554A3 (en) * 2006-04-10 2011-07-13 Imec A method to create super secondary grain growth in narrow trenches
JP2008013848A (en) * 2006-06-08 2008-01-24 Tokyo Electron Ltd Film-forming apparatus and film-forming method
JP5145225B2 (en) * 2006-07-14 2013-02-13 株式会社アルバック Manufacturing method of semiconductor device
JP4910560B2 (en) * 2006-08-11 2012-04-04 ソニー株式会社 Semiconductor device and manufacturing method thereof
JP2008047719A (en) * 2006-08-17 2008-02-28 Sony Corp Method for manufacturing semiconductor device
JP4740071B2 (en) * 2006-08-31 2011-08-03 株式会社東芝 Semiconductor device
JP4321570B2 (en) * 2006-09-06 2009-08-26 ソニー株式会社 Manufacturing method of semiconductor device
JP2008091645A (en) * 2006-10-02 2008-04-17 Tokyo Electron Ltd Semiconductor manufacturing apparatus, semiconductor device manufacturing method, and storage medium
EP2014787B1 (en) * 2006-10-03 2017-09-06 JX Nippon Mining & Metals Corporation Cu-Mn ALLOY SPUTTERING TARGET
JP4740083B2 (en) * 2006-10-05 2011-08-03 株式会社東芝 Semiconductor device and manufacturing method thereof
JP5076452B2 (en) * 2006-11-13 2012-11-21 富士通セミコンダクター株式会社 Manufacturing method of semiconductor device
JP2008135569A (en) * 2006-11-28 2008-06-12 Rohm Co Ltd Method of manufacturing semiconductor device, and semiconductor device
JP5010265B2 (en) * 2006-12-18 2012-08-29 株式会社東芝 Manufacturing method of semiconductor device
JP5103914B2 (en) 2007-01-31 2012-12-19 富士通セミコンダクター株式会社 Semiconductor device manufacturing method and semiconductor device
DE102007004860B4 (en) * 2007-01-31 2008-11-06 Advanced Micro Devices, Inc., Sunnyvale A method of making a copper-based metallization layer having a conductive overcoat by an improved integration scheme
JP4110192B1 (en) 2007-02-23 2008-07-02 キヤノン株式会社 Photoelectric conversion device and imaging system using photoelectric conversion device
JP4324617B2 (en) 2007-02-26 2009-09-02 東京エレクトロン株式会社 Sputter deposition method and sputter deposition apparatus
JP5141683B2 (en) 2007-03-27 2013-02-13 富士通セミコンダクター株式会社 Manufacturing method of semiconductor device
JP4453845B2 (en) * 2007-04-10 2010-04-21 国立大学法人東北大学 Liquid crystal display device and manufacturing method thereof
US7633164B2 (en) 2007-04-10 2009-12-15 Tohoku University Liquid crystal display device and manufacturing method therefor
JP5089244B2 (en) 2007-05-22 2012-12-05 ローム株式会社 Semiconductor device
JP5196467B2 (en) * 2007-05-30 2013-05-15 東京エレクトロン株式会社 Semiconductor device manufacturing method, semiconductor manufacturing apparatus, and storage medium
JP2008300568A (en) * 2007-05-30 2008-12-11 Tokyo Electron Ltd Method of manufacturing semiconductor device, semiconductor manufacturing equipment, and storage medium
JP2009016782A (en) 2007-06-04 2009-01-22 Tokyo Electron Ltd Film forming method, and film forming apparatus
JP2009004518A (en) * 2007-06-20 2009-01-08 Kobe Steel Ltd Thin film transistor substrate and display device
WO2009001780A1 (en) * 2007-06-22 2008-12-31 Rohm Co., Ltd. Semiconductor device and method for manufacturing the same
JP5288734B2 (en) * 2007-06-22 2013-09-11 ローム株式会社 Semiconductor device and manufacturing method thereof
EP2162906B1 (en) * 2007-06-29 2013-10-02 Imec A method for producing a copper contact
JP2009076881A (en) * 2007-08-30 2009-04-09 Tokyo Electron Ltd Treatment gas supply system and processing device
JPWO2009038168A1 (en) * 2007-09-21 2011-01-06 東京エレクトロン株式会社 Film forming apparatus and film forming method
US7884475B2 (en) * 2007-10-16 2011-02-08 International Business Machines Corporation Conductor structure including manganese oxide capping layer
US20090117731A1 (en) * 2007-11-01 2009-05-07 Taiwan Semiconductor Manufacturing Co., Ltd. Semiconductor interconnection structure and method for making the same
US8168532B2 (en) * 2007-11-14 2012-05-01 Fujitsu Limited Method of manufacturing a multilayer interconnection structure in a semiconductor device
JP2009135139A (en) 2007-11-28 2009-06-18 Toshiba Corp Semiconductor device and method of manufacturing the same
JP2009141058A (en) * 2007-12-05 2009-06-25 Fujitsu Microelectronics Ltd Semiconductor device and method of manufacturing the same
JP2009147137A (en) 2007-12-14 2009-07-02 Toshiba Corp Semiconductor device and method of fabricating the same
JP5264187B2 (en) * 2008-01-08 2013-08-14 パナソニック株式会社 Semiconductor device and manufacturing method thereof
JP5366235B2 (en) 2008-01-28 2013-12-11 東京エレクトロン株式会社 Semiconductor device manufacturing method, semiconductor manufacturing apparatus, and storage medium
WO2009107205A1 (en) 2008-02-27 2009-09-03 富士通マイクロエレクトロニクス株式会社 Semiconductor device and method for manufacturing the same
JP5343369B2 (en) 2008-03-03 2013-11-13 東京エレクトロン株式会社 Semiconductor device manufacturing method, semiconductor manufacturing apparatus, and storage medium
WO2009117670A2 (en) * 2008-03-21 2009-09-24 President And Fellows Of Harvard College Self-aligned barrier layers for interconnects
JP4423379B2 (en) 2008-03-25 2010-03-03 合同会社先端配線材料研究所 Copper wiring, semiconductor device, and method of forming copper wiring
JP5441345B2 (en) * 2008-03-27 2014-03-12 富士フイルム株式会社 Polishing liquid and polishing method
JP5343417B2 (en) 2008-06-25 2013-11-13 富士通セミコンダクター株式会社 Semiconductor device and manufacturing method thereof
JP5417754B2 (en) * 2008-07-11 2014-02-19 東京エレクトロン株式会社 Film forming method and processing system
JP2010050359A (en) * 2008-08-22 2010-03-04 Rohm Co Ltd Method of manufacturing semiconductor device
JP2010080606A (en) * 2008-09-25 2010-04-08 Rohm Co Ltd Method of manufacturing semiconductor apparatus
JP2010073736A (en) * 2008-09-16 2010-04-02 Rohm Co Ltd Method of manufacturing semiconductor device
US8039390B2 (en) 2008-08-05 2011-10-18 Rohm Co., Ltd. Method of manufacturing semiconductor device
US8110504B2 (en) 2008-08-05 2012-02-07 Rohm Co., Ltd. Method of manufacturing semiconductor device
JP5353109B2 (en) * 2008-08-15 2013-11-27 富士通セミコンダクター株式会社 Manufacturing method of semiconductor device
US8258626B2 (en) 2008-09-16 2012-09-04 Advanced Interconnect Materials, Llc Copper interconnection, method for forming copper interconnection structure, and semiconductor device
JP4415100B1 (en) 2008-12-19 2010-02-17 国立大学法人東北大学 Copper wiring, semiconductor device, and copper wiring forming method
JP4441658B1 (en) 2008-12-19 2010-03-31 国立大学法人東北大学 Copper wiring forming method, copper wiring, and semiconductor device
US8013444B2 (en) * 2008-12-24 2011-09-06 Intel Corporation Solder joints with enhanced electromigration resistance
JP2010171362A (en) * 2008-12-26 2010-08-05 Fujifilm Corp Cleaning agent for semiconductor device and method for manufacturing the semiconductor device using the same
JP2010171398A (en) * 2008-12-26 2010-08-05 Toshiba Corp Method for manufacturing semiconductor device
JP2010171063A (en) * 2009-01-20 2010-08-05 Kobe Steel Ltd Method of manufacturing semiconductor wiring
JP2010177393A (en) * 2009-01-29 2010-08-12 Sony Corp Semiconductor storage device and method of manufacturing the same
KR101558428B1 (en) 2009-03-03 2015-10-20 삼성전자주식회사 Method of forming semiconductor device
JP5411535B2 (en) * 2009-03-11 2014-02-12 東京エレクトロン株式会社 Manufacturing method of semiconductor device
JP5530118B2 (en) * 2009-04-08 2014-06-25 東京エレクトロン株式会社 Method for forming manganese oxide film, method for manufacturing semiconductor device, and semiconductor device
JP5190415B2 (en) 2009-06-04 2013-04-24 パナソニック株式会社 Semiconductor device
JP5487748B2 (en) 2009-06-16 2014-05-07 東京エレクトロン株式会社 Barrier layer, film forming method and processing system
JP5522979B2 (en) 2009-06-16 2014-06-18 国立大学法人東北大学 Film forming method and processing system
JP5466889B2 (en) * 2009-06-18 2014-04-09 東京エレクトロン株式会社 Method for forming multilayer wiring
US8168528B2 (en) * 2009-06-18 2012-05-01 Kabushiki Kaisha Toshiba Restoration method using metal for better CD controllability and Cu filing
US8134234B2 (en) * 2009-06-18 2012-03-13 Kabushiki Kaisha Toshiba Application of Mn for damage restoration after etchback
JP5359642B2 (en) 2009-07-22 2013-12-04 東京エレクトロン株式会社 Deposition method
JP5481989B2 (en) * 2009-07-22 2014-04-23 富士通セミコンダクター株式会社 Manufacturing method of semiconductor device
JP5616605B2 (en) * 2009-10-16 2014-10-29 株式会社アルバック Method for forming copper thin film
KR101770537B1 (en) * 2009-10-23 2017-08-22 프레지던트 앤드 펠로우즈 오브 하바드 칼리지 Self-aligned barrier and capping layers for interconnects
JP5560696B2 (en) * 2009-12-21 2014-07-30 富士通セミコンダクター株式会社 Manufacturing method of semiconductor device
JP5440221B2 (en) * 2010-02-02 2014-03-12 日本電気株式会社 Manufacturing method of laminated structure of semiconductor device
US8377823B2 (en) * 2010-02-17 2013-02-19 Renesas Electronics Corporation Semiconductor device including porous layer covered by poreseal layer
JP2011216862A (en) 2010-03-16 2011-10-27 Tokyo Electron Ltd Deposition method and apparatus
US8377822B2 (en) 2010-05-21 2013-02-19 Kabushiki Kaisha Toshiba Semiconductor device and manufacturing method thereof
US20110290308A1 (en) * 2010-05-28 2011-12-01 General Electric Company Monolithically integrated solar modules and methods of manufacture
JP5429078B2 (en) 2010-06-28 2014-02-26 東京エレクトロン株式会社 Film forming method and processing system
JP5403527B2 (en) * 2010-07-02 2014-01-29 合同会社先端配線材料研究所 Semiconductor device
US8492289B2 (en) * 2010-09-15 2013-07-23 International Business Machines Corporation Barrier layer formation for metal interconnects through enhanced impurity diffusion
US9064875B2 (en) 2010-09-29 2015-06-23 Infineon Technologies Ag Semiconductor structure and method for making same
US8461683B2 (en) * 2011-04-01 2013-06-11 Intel Corporation Self-forming, self-aligned barriers for back-end interconnects and methods of making same
JP2013080779A (en) * 2011-10-03 2013-05-02 Ulvac Japan Ltd Semiconductor device manufacturing method and semiconductor device
DE102012110060A1 (en) * 2011-11-21 2013-05-23 Infineon Technologies Ag Making semiconductor structure, comprises forming first opening in dielectric layer, forming opening in dielectric material, forming seed layer within first opening, forming masking layer, and forming fill layer over seed layer
WO2013125449A1 (en) * 2012-02-22 2013-08-29 東京エレクトロン株式会社 Semiconductor-device manufacturing method, storage medium, and semiconductor device
JP5475820B2 (en) * 2012-03-23 2014-04-16 株式会社東芝 Manufacturing method of semiconductor device
JPWO2013153777A1 (en) 2012-04-11 2015-12-17 東京エレクトロン株式会社 Semiconductor device manufacturing method, semiconductor device, and semiconductor manufacturing apparatus
JP5554364B2 (en) * 2012-04-12 2014-07-23 Ｊｘ日鉱日石金属株式会社 Copper alloy wiring for semiconductor, sputtering target, and method for forming copper alloy wiring for semiconductor
US9076661B2 (en) 2012-04-13 2015-07-07 Applied Materials, Inc. Methods for manganese nitride integration
US9048294B2 (en) 2012-04-13 2015-06-02 Applied Materials, Inc. Methods for depositing manganese and manganese nitrides
US8969197B2 (en) 2012-05-18 2015-03-03 International Business Machines Corporation Copper interconnect structure and its formation
US9054109B2 (en) * 2012-05-29 2015-06-09 International Business Machines Corporation Corrosion/etching protection in integration circuit fabrications
TW201403782A (en) * 2012-07-04 2014-01-16 Ind Tech Res Inst Method for manufacturing through substrate via structure, through substrate via structure and control method of TSV capacitance
US9281263B2 (en) 2012-07-17 2016-03-08 Taiwan Semiconductor Manufacturing Co., Ltd. Interconnect structure including a continuous conductive body
US8735278B2 (en) * 2012-07-17 2014-05-27 Taiwan Semiconductor Manufactring Co., Ltd. Copper etch scheme for copper interconnect structure
WO2014013941A1 (en) * 2012-07-18 2014-01-23 東京エレクトロン株式会社 Method for manufacturing semiconductor device
US8765602B2 (en) 2012-08-30 2014-07-01 International Business Machines Corporation Doping of copper wiring structures in back end of line processing
JP5374779B1 (en) * 2013-02-12 2013-12-25 国立大学法人東北大学 SOLAR CELL, METHOD FOR FORMING OXIDE LAYER IN THE SOLAR CELL, METHOD FOR FORMING LAMINATED OXIDE LAYER
US9190321B2 (en) 2013-04-08 2015-11-17 International Business Machines Corporation Self-forming embedded diffusion barriers
TWI609095B (en) * 2013-05-30 2017-12-21 應用材料股份有限公司 Methods for manganese nitride integration
JP2015079901A (en) * 2013-10-18 2015-04-23 株式会社東芝 Semiconductor device and method of manufacturing semiconductor device
JP5735093B1 (en) 2013-12-24 2015-06-17 株式会社マテリアル・コンセプト Solar cell and manufacturing method thereof
JP5694503B2 (en) * 2013-12-27 2015-04-01 Jx日鉱日石金属株式会社 SEED LAYER WITH SELF-DIFFUSION SUPPRESSING FUNCTION AND METHOD FOR FORMING SEED LAYER HAVING SELF-DIFFUSION SUPPRESSING FUNCTION
US9263389B2 (en) 2014-05-14 2016-02-16 International Business Machines Corporation Enhancing barrier in air gap technology
US9613906B2 (en) * 2014-06-23 2017-04-04 GlobalFoundries, Inc. Integrated circuits including modified liners and methods for fabricating the same
US9455182B2 (en) 2014-08-22 2016-09-27 International Business Machines Corporation Interconnect structure with capping layer and barrier layer
US9425093B2 (en) * 2014-12-05 2016-08-23 Tokyo Electron Limited Copper wiring forming method, film forming system, and storage medium
JP6484490B2 (en) * 2015-04-10 2019-03-13 ルネサスエレクトロニクス株式会社 Semiconductor device and manufacturing method thereof
US9842805B2 (en) 2015-09-24 2017-12-12 International Business Machines Corporation Drive-in Mn before copper plating
US10229851B2 (en) 2016-08-30 2019-03-12 International Business Machines Corporation Self-forming barrier for use in air gap formation
US10204829B1 (en) 2018-01-12 2019-02-12 International Business Machines Corporation Low-resistivity metallic interconnect structures with self-forming diffusion barrier layers
US10840325B2 (en) 2018-04-11 2020-11-17 International Business Machines Corporation Low resistance metal-insulator-metal capacitor electrode
US11133216B2 (en) 2018-06-01 2021-09-28 International Business Machines Corporation Interconnect structure
US11846018B2 (en) 2021-02-08 2023-12-19 Macdermid Enthone Inc. Method and wet chemical compositions for diffusion barrier formation

Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0262035A (en) 1988-08-29 1990-03-01 Nippon Telegr & Teleph Corp <Ntt> Semiconductor device
JPH0547760A (en) 1991-08-12 1993-02-26 Hitachi Ltd Semiconductor integrated circuit device and its manufacture and sputtering target for the manufacture
JPH05102318A (en) 1991-04-05 1993-04-23 Internatl Business Mach Corp <Ibm> Method and apparatus for forming conductive copper alloy plug
JPH06310609A (en) 1993-02-17 1994-11-04 Hyundai Electron Ind Co Ltd Manufacture of metal plug
JPH08115914A (en) 1994-10-14 1996-05-07 Hitachi Ltd Semiconductor device
JPH08139092A (en) 1994-02-21 1996-05-31 Toshiba Corp Semiconductor device and manufacture thereof
JPH1154458A (en) 1997-05-08 1999-02-26 Applied Materials Inc Metallization structure
JPH1187394A (en) 1997-09-09 1999-03-30 Saitama Nippon Denki Kk Cob-mounting board and method for mounting ic chip on the board
JPH1187349A (en) 1997-07-16 1999-03-30 Mitsubishi Electric Corp Production of semiconductor device and the semiconductor device
JPH11186273A (en) 1997-12-19 1999-07-09 Ricoh Co Ltd Semiconductor device and manufacture thereof
JP2000174023A (en) 1998-12-04 2000-06-23 Nec Corp Semiconductor device and manufacture thereof
JP2000260865A (en) 1999-03-08 2000-09-22 Tori Chemical Kenkyusho:Kk Wiring film formation method and wiring film structure
JP2001044156A (en) 1999-07-26 2001-02-16 Nec Corp Manufacture of semiconductor device and chemical polishing apparatus
WO2001013415A1 (en) 1999-08-11 2001-02-22 Tokyo Electron Limited Production method of semiconductor device and production device therefor
JP2002026568A (en) 2000-07-10 2002-01-25 Kumagai Gumi Co Ltd Sheet material
JP2003142579A (en) 2001-11-07 2003-05-16 Hitachi Ltd Semiconductor device and method for manufacturing the same
JP2003529206A (en) 1999-11-24 2003-09-30 ハネウェル・インターナショナル・インコーポレーテッド Physical vapor deposition targets, conductive integrated circuit metal alloy interconnects, electroplated anodes, metal alloys for use as conductive interconnects in integrated circuits
US20030207561A1 (en) * 2002-05-03 2003-11-06 Dubin Valery M. Interconnect structures containing conductive electrolessly deposited etch stop layers, liner layers, and via plugs
US6664185B1 (en) 2002-04-25 2003-12-16 Advanced Micro Devices, Inc. Self-aligned barrier formed with an alloy having at least two dopant elements for minimized resistance of interconnect
US6706629B1 (en) * 2003-01-07 2004-03-16 Taiwan Semiconductor Manufacturing Company Barrier-free copper interconnect
JP2005277390A (en) 2004-02-27 2005-10-06 Handotai Rikougaku Kenkyu Center:Kk Semiconductor device and its manufacturing method
US7078336B2 (en) 2003-11-19 2006-07-18 Taiwan Semiconductor Manufacturing Co., Ltd. Method and system for fabricating a copper barrier layer with low dielectric constant and leakage current

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002046249A2 (en) * 2000-11-07 2002-06-13 Symyx Technologies, Inc. Methods of copolymerizing ethylene and isobutylene and polymers made thereby
US20020081845A1 (en) * 2000-12-27 2002-06-27 Novellus Systems, Inc. Method for the formation of diffusion barrier
US7271103B2 (en) * 2003-10-17 2007-09-18 Taiwan Semiconductor Manufacturing Co., Ltd. Surface treated low-k dielectric as diffusion barrier for copper metallization
US6998343B1 (en) * 2003-11-24 2006-02-14 Lsi Logic Corporation Method for creating barrier layers for copper diffusion
JP2009135139A (en) 2007-11-28 2009-06-18 Toshiba Corp Semiconductor device and method of manufacturing the same
JP2009147137A (en) 2007-12-14 2009-07-02 Toshiba Corp Semiconductor device and method of fabricating the same

Patent Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0262035A (en) 1988-08-29 1990-03-01 Nippon Telegr & Teleph Corp <Ntt> Semiconductor device
JPH05102318A (en) 1991-04-05 1993-04-23 Internatl Business Mach Corp <Ibm> Method and apparatus for forming conductive copper alloy plug
JPH0547760A (en) 1991-08-12 1993-02-26 Hitachi Ltd Semiconductor integrated circuit device and its manufacture and sputtering target for the manufacture
JPH06310609A (en) 1993-02-17 1994-11-04 Hyundai Electron Ind Co Ltd Manufacture of metal plug
JPH08139092A (en) 1994-02-21 1996-05-31 Toshiba Corp Semiconductor device and manufacture thereof
KR100203536B1 (en) 1994-02-21 1999-06-15 니시무로 타이죠 A semiconductor device
JPH08115914A (en) 1994-10-14 1996-05-07 Hitachi Ltd Semiconductor device
JPH1154458A (en) 1997-05-08 1999-02-26 Applied Materials Inc Metallization structure
JPH1187349A (en) 1997-07-16 1999-03-30 Mitsubishi Electric Corp Production of semiconductor device and the semiconductor device
JPH1187394A (en) 1997-09-09 1999-03-30 Saitama Nippon Denki Kk Cob-mounting board and method for mounting ic chip on the board
JPH11186273A (en) 1997-12-19 1999-07-09 Ricoh Co Ltd Semiconductor device and manufacture thereof
JP2000174023A (en) 1998-12-04 2000-06-23 Nec Corp Semiconductor device and manufacture thereof
JP2000260865A (en) 1999-03-08 2000-09-22 Tori Chemical Kenkyusho:Kk Wiring film formation method and wiring film structure
JP2001044156A (en) 1999-07-26 2001-02-16 Nec Corp Manufacture of semiconductor device and chemical polishing apparatus
WO2001013415A1 (en) 1999-08-11 2001-02-22 Tokyo Electron Limited Production method of semiconductor device and production device therefor
JP2003529206A (en) 1999-11-24 2003-09-30 ハネウェル・インターナショナル・インコーポレーテッド Physical vapor deposition targets, conductive integrated circuit metal alloy interconnects, electroplated anodes, metal alloys for use as conductive interconnects in integrated circuits
JP2002026568A (en) 2000-07-10 2002-01-25 Kumagai Gumi Co Ltd Sheet material
JP2003142579A (en) 2001-11-07 2003-05-16 Hitachi Ltd Semiconductor device and method for manufacturing the same
US6664185B1 (en) 2002-04-25 2003-12-16 Advanced Micro Devices, Inc. Self-aligned barrier formed with an alloy having at least two dopant elements for minimized resistance of interconnect
US20030207561A1 (en) * 2002-05-03 2003-11-06 Dubin Valery M. Interconnect structures containing conductive electrolessly deposited etch stop layers, liner layers, and via plugs
US6706629B1 (en) * 2003-01-07 2004-03-16 Taiwan Semiconductor Manufacturing Company Barrier-free copper interconnect
US7078336B2 (en) 2003-11-19 2006-07-18 Taiwan Semiconductor Manufacturing Co., Ltd. Method and system for fabricating a copper barrier layer with low dielectric constant and leakage current
JP2005277390A (en) 2004-02-27 2005-10-06 Handotai Rikougaku Kenkyu Center:Kk Semiconductor device and its manufacturing method

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Kagaku Binran Basic II" edited by The Chemical Society of Japan (issued by Maruzen Co., Ltd. on Aug. 20, 1970, third edition), p. 1132-1133.
U.S. Appl. No. 12/276,796, filed Nov. 24, 2008, Usui, et al.
U.S. Appl. No. 12/332,583, filed Dec. 11, 2008, Watanabe, et al.
W. A. Lanford, et al., "Low-temperature passivation of copper by doping with Al or Mg", Thin Solid Films, vol. 262, 1995, pp. 234-241.

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10158005B2 (en) 2008-11-07 2018-12-18 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device
US10056494B2 (en) 2009-11-13 2018-08-21 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device and manufacturing method thereof
US10516055B2 (en) 2009-11-13 2019-12-24 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device and manufacturing method thereof
US10944010B2 (en) 2009-11-13 2021-03-09 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device
US11456385B2 (en) 2009-11-13 2022-09-27 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device and manufacturing method thereof
US11955557B2 (en) 2009-11-13 2024-04-09 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device and manufacturing method thereof
US9978878B2 (en) 2010-04-23 2018-05-22 Semiconductor Energy Laboratory Co., Ltd. Manufacturing method of semiconductor device
US8836124B2 (en) 2012-03-08 2014-09-16 International Business Machines Corporation Fuse and integrated conductor
US11430817B2 (en) 2013-11-29 2022-08-30 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device

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